CN109250728A - The Cu-SAPO molecular sieve and application of Cu-SAPO Zeolite synthesis method and synthesis - Google Patents

The Cu-SAPO molecular sieve and application of Cu-SAPO Zeolite synthesis method and synthesis Download PDF

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CN109250728A
CN109250728A CN201710566426.7A CN201710566426A CN109250728A CN 109250728 A CN109250728 A CN 109250728A CN 201710566426 A CN201710566426 A CN 201710566426A CN 109250728 A CN109250728 A CN 109250728A
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sapo
molecular sieve
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copper
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CN109250728B (en
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杨淼
孙丽婧
田鹏
刘中民
曹毅
向骁
桑石云
曹磊
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Dalian Institute of Chemical Physics of CAS
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Abstract

The present invention relates to a kind of method for synthesizing Cu-SAPO molecular sieve and products thereof and purposes.More particularly, to method include that Cu-SAPO molecular sieve that copper-amine complex is the high Cu content of template synthesis will be used as the source Cu and part silicon phosphorus silicon source and crystal seed, the synthesis of progress Cu-SAPO molecular sieve.This method can not only control the copper content in SAPO molecular sieve in a wider range, can be distributed with Effective Regulation silicone content and its silicon atom, product yield is high.Gained Cu-SAPO molecular sieve catalyst shows excellent high-temperature hydrothermal stability and to NOxCatalysis selective reduction removal performance.

Description

The Cu-SAPO molecular sieve and application of Cu-SAPO Zeolite synthesis method and synthesis
Technical field
The invention belongs to chemical fields, are related to molecular sieve and preparation method thereof field more particularly to a kind of synthesis Cu- The method of SAPO (cupric phosphor-silicon-aluminum molecular sieve) and the product and application thereof obtained by this method.The Cu-SAPO can be used for The catalyst of oxynitrides purification process.
Background technique
1984, U.S. combinating carbide company (UCC) developed series by PO2 +、AlO2 -And SiO2Tetrahedron constitutes three Tie up the novel phosphoric acid Si-Al molecular sieve (SAPO-n) (USP 4,440,871) of open-framework structure.Si atom is by way of substitution Into neutral aluminum phosphate skeleton structure, skeleton is made to generate net negative electrical charge, cause Bronsted acidity, thus assigned SAPO molecular sieve and urge Change performance.(SSZ-13 is that have with SAPO-34 to Cu-SAPO-34 the or Cu-SSZ-13 catalyst prepared using SAPO-34 as carrier The molecular sieve of identical topological structure, difference are that the former is Si-Al molecular sieve, and the latter is silicoaluminophosphamolecular molecular sieves) in the diesel oil tailstock During gas selective catalysis reduction technique (Urea-SCR) system purification oxynitrides, have high activity and excellent hydro-thermal steady It is qualitative.The introducing overwhelming majority of copper ion uses ion-exchange, i.e., the molecule that will be obtained in SAPO molecular sieve catalyst at present First roasting removes template to sieve, and the ammonia pattern product that obtain are swapped with ammonium nitrate solution, then molten with certain density mantoquita again A few hours are mixed in liquid, are filtered, washed, dry, obtain Cu-SAPO-34 after high-temperature roasting.Due to SAPO molecular sieve have compared with The low-temperature hydrothermal stability of difference, partial hydrolysis, which often occurs, for framework of molecular sieve in ion exchange process leads to molecular sieve specific surface Product decline.Meanwhile ion-exchange process is cumbersome, the utilization rate of copper ion is low in copper salt solution in exchange process, washed Journey expends a large amount of pure water and is converted to sewage, high-temperature calcination process time consumption and energy consumption.
Compared to ion-exchange, one-step synthesis method cupric molecular sieve has a clear superiority.CN 102259892A discloses one Kind avoids cumbersome ion exchange using metal-amine complex as the method for template agent synthesized silicon-aluminum phosphate molecular sieve catalyst Technique.But the high-temperature hydrothermal stability of the Cu-SAPO-34 of one-step synthesis is poor, limits its industrial application.Such as Corma with Copper-amine complex and diethylamine are that template synthesizes Cu-SAPO-34 molecular sieve, and copper load capacity is controlled in 3.4-10.4%, crystal About 6-10 μm of granularity.Studies have shown that the low copper load capacity catalyst (copper content 3.4%) of this method synthesis is old through 750 DEG C of hydro-thermals Activity is decreased obviously after changing 13h, and the Cu-SAPO-34 of (copper content 6.0%) in having, high (10.4%) copper content is urged Agent, 750 DEG C of hydrothermal aging 13h back skeleton structures all collapse (Applied CatalysisB:Environmental, 2012,127:273).In addition to Cu load capacity influences hydrothermal stability of molecular sieve, the distribution of skeleton negative electrical charge also influences the outer copper of skeleton The stability of ion, to influence the hydrothermal stability of copper load molecular sieve sample.For SAPO molecular sieve, skeleton negative electrical charge Amount and distribution are directly derived from the introduction volume and its distribution of silicon atom.As the single substitution P atom of Si atom can form Si (4Al) even It connects, forms acid site.And when Si atom while replacing the adjacent P and Al atomic time, it just will form the rich region Si even silicon island, lead The uneven distribution of skeleton negative electrical charge is caused, this is unfavorable for being stabilized for copper ion.In order to be further improved synthesis Cu-SAPO- The hydrothermal stability of 34 molecular sieves, a lot of research work are attempted to compound synthesis with copper-amine complex using various organic formwork agents Cu-SAPO-34, in its copper content of modulation and molecular sieve silicon amount and silicon atom distribution (J.Catalysis 2014,314, 73-82；Chemical Engineering Journal 2016,294,254-263；CN 104209141A；CN 103818927A).These work show that copper-amine complex is easy to make to generate silicon in SAPO molecular sieve skeleton as synthesis template Island.But if in order to avoid silicon island is formed and controls copper load capacity, while reducing the amount of copper-amine complex template and silicon source, again It will affect product yield and crystallinity.
Summary of the invention
To solve the above problems, the application uses copper-amine complex to obtain high copper content as synthesis template first Then it is carried out the synthesis of Cu-SAPO molecular sieve directly as the source Cu, part silicon phosphorus silicon source and crystal seed by Cu-SAPO.It should Method avoids when directly use copper-amine complex and other templates as templated synthesis Cu-SAPO is total to, copper-amine complex and The competition of other synthesis templates, preferably plays guiding role of other organic formwork agents in synthesis, and zeolite product Crystal size, Cu content and silicone content and distribution can obtain Effective Regulation, thus obtain cupric molecular sieve have more Excellent catalytic performance and hydrothermal stability.
In one aspect, the present invention provides a kind of synthetic method of Cu-SAPO molecular sieve, which is characterized in that including as follows Step:
(1) using the Cu-SAPO molecular sieve of the template synthesis high copper content comprising copper-amine complex, Cu load capacity is 5-20wt%, preferably 5-15wt%；
(2) organic amine template R and water and optional silicon source, silicon source and phosphorus source are mixed to prepare crystallization liquid；
(3) using the Cu-SAPO molecular sieve of high copper content obtained in step (1) as obtained in raw material and step (2) Crystallization liquid mixes and carries out hydrothermal crystallizing, obtains Cu-SAPO zeolite product.
Optionally, the Cu-SAPO Molecular sieve raw material in step (1) be use copper-amine complex as single template or with have Machine amine template R1 is together as mixed templates, the Cu-SAPO synthesized by silicon source, silicon source, phosphorus source and water by hydrothermal crystallizing, Wherein silicon source can be selected from one or more of ethyl orthosilicate, silica solution and white carbon black；Silicon source can selected from aluminium isopropoxide, One or more of boehmite, Aluminum sol and aluminium hydroxide；Phosphorus source can be selected from phosphoric acid, phosphorous acid and phosphorus pentoxide One or more of；Organic amine template R1 can selected from triethylamine, diethylamine, morpholine, tetraethyl ammonium hydroxide, propylamine and The mixing of one or more of piperazine.
Optionally, in step (1) for synthesize the silicon source of Cu-SAPO Molecular sieve raw material, phosphorus source, silicon source, copper-amine complex, The molar ratio of organic amine template R1 and water is Al2O3:P2O5:SiO2:Cu:R1:H2O=1:0.8~1:0.3~1.0:0.1 ~0.8:0-3.5:40~80.
Optionally, the copper-amine complex in step (1) includes copper-polyethylene polyamine complex compound, preferably Cu- tetraethylenepentamine Complex compound, Cu- triethylene tetramine complex compound, Cu- diethylenetriamine complex compound and Cu- pentaethylene hexamine complex compound.
Optionally, the synthesis of the Cu-SAPO molecular sieve of high copper content carries out in the presence of SAPO crystal seed in step (1).
Optionally, silicon source used in step (2) can selected from one of ethyl orthosilicate, silica solution and white carbon black or It is several；Silicon source can be selected from one or more of aluminium isopropoxide, boehmite, Aluminum sol and aluminium hydroxide；Phosphorus source can be with Selected from one or more of phosphoric acid, phosphorous acid and phosphorus pentoxide；Organic amine template R can selected from triethylamine, diethylamine, The mixing of one or more of morpholine, tetraethyl ammonium hydroxide, propylamine and piperazine.
Optionally, the molar ratio of silicon source, phosphorus source used in step (2), silicon source, organic amine template R and water is Al2O3:P2O5:SiO2:R:H2O=1:0.5~2:0.01~1.5:0.5~10:15~200, preferably Al2O3:P2O5:SiO2: R:H2O=1:0.7~1.5:0.1~1.0:1~5:30~100.
Optionally, the inventory of the Cu-SAPO raw material of high copper content is solid oxidation amount of substance in crystallization liquid in step (3) The 2-200wt% of summation.
Optionally, the temperature that hydrothermal crystallizing is carried out in step (3) is 140-240 DEG C, and the time is 0.5~72 hour.It is more excellent The crystallization temperature of choosing is 150-200 DEG C.
Optionally, the Cu load capacity of the Cu-SAPO zeolite product prepared in step (3) and the Cu-SAPO of high copper content The copper content of raw material is compared to 10% or more decline, the preferably 10-70% of the copper content of the Cu-SAPO raw material of high copper content.
Optionally, the Cu-SAPO molecular sieve includes Cu-SAPO-34 molecular sieve, Cu-SAPO-42 molecular sieve, Cu-DNL- Any one of 6 (RHO).
On the other hand, the present invention provides a kind of Cu-SAPO molecular screen primary powder prepared by the above method, preferably Cu- SAPO-34 molecular screen primary powder, is rhombohedron shape, and preferable particle size range is 1-2 μm.
On the other hand, the present invention also provides one kind to be used for NOxThe catalyst of selective reduction elimination reaction, by according to above-mentioned The molecular sieve of method synthesis is obtained through roasting in 500~800 DEG C of air.The catalyst is especially de- in the catalysis of nitrogen oxides Except showing good catalytic performance in reaction.Catalyst activity after 800 DEG C of processing in saturated steam 16 hours still maintains.
On the other hand, the present invention provides a kind of method for improving Cu-SAPO molecular sieve high-temperature hydrothermal stability, It is characterized in that, which comprises will be by using the Cu-SAPO of the high copper content of the template synthesis comprising copper-amine complex Molecular sieve mixes with crystallization liquid and carries out hydrothermal crystallizing, wherein the crystallization liquid be by by organic amine template R and water and Prepared by optional silicon source, silicon source and phosphorus source mixing.
The present invention can produce at least one of following beneficial effect:
(1) a kind of new method for synthesizing Cu-SAPO molecular sieve is provided, the method is realized with high hydrothermal stability Cu- The efficient utilization of the high yield synthesis and the source Cu of SAPO.Its crystal size, Cu content and silicone content and distribution are available effectively Regulation；
(2) molecular sieve prepared by can be used as catalytic eliminating of the catalyst for nitrogen oxides and react, and show good Catalytic performance.Catalyst still has promotion through 800 DEG C of catalytic performances after steam treatment 16 hours or remains unchanged.
Detailed description of the invention
Fig. 1 is the XRD spectrum of the high copper content Cu-SAPO-34 synthesized in embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of the high copper content Cu-SAPO-34 synthesized in embodiment 1.
Fig. 3 is the XRD spectrum of 3 product of embodiment.
The scanning electron microscope (SEM) photograph (SEM) of 5 product of Fig. 4 embodiment.
Fig. 5 is the solid of embodiment 329Si nuclear magnetic spectrogram.
Fig. 6 is the NH of embodiment 3,5,83- SCR reaction evaluating result.
Fig. 7 be 5 catalyst of embodiment through (embodiment 5) before High-temperature water heat treatment, after (embodiment 5-H) sample NH3- SCR reaction evaluating Comparative result.
Fig. 8 is the XRD spectrum of 12 sample of embodiment.
Fig. 9 is the XRD spectrum of 13 sample of embodiment.
Figure 10 is the scanning electron microscope (SEM) photograph (SEM) of 14 product of embodiment.
Figure 11 is the SEM electromicroscopic photograph of 3 sample of comparative example.
The solid of 3 sample of Figure 12 comparative example29Si nuclear magnetic spectrogram.
Specific embodiment
Below with reference to embodiment, the present invention is further explained.It should be understood that these embodiments be merely to illustrate the present invention without For limiting the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to normal condition or According to the normal condition proposed by manufacturer.In the case where not doing specified otherwise, raw material used in this application passes through commercial sources Purchase, not specially treated direct use.Cu-SAPO-34 Molecular sieve raw material is that copper-amine complex is used to close as single template At or with other organic amines together as mixed templates one-step synthesis high copper content Cu-SAPO-34, Cu load capacity be 5- 20wt%.127 (2012) 273-280 of synthetic method bibliography Applied Catalysis B:Environmental, but Method without being limited thereto.
In the case where not doing specified otherwise, the test condition of the application is as follows:
Element composition is measured using the 2424 X-type ray fluorescence analysis instrument (XRF) of Magix of Philips company.
X-ray powder diffraction material phase analysis (XRD) uses X ' the Pert PRO of Dutch Panaco (PANalytical) company X-ray diffractometer, Cu target, K α radiation source (λ=0.15418nm), voltage 40KV, electric current 40mA.
Specific surface area and hole using 2020 type physical adsorption appearance of Micromeritics company of U.S. ASAP measurement sample Diameter distribution.Before analysis, sample vacuumizes heat pre-treatment 6h at 350 DEG C, using He as Medium Measurement sample cell free volume.Point When analysing sample, using nitrogen as adsorbed gas, physical absorption and desorption measurement are carried out at liquid nitrogen temperature (77K).Using BET formula Determine the specific surface area of material；Use relative pressure (P/P0) be 0.99 when N2Adsorbance calculate material total pore volume.Use t- Plot method calculates micro pore surface area and Micropore volume.When calculating, N2Molecular cross-sectional area takes 0.162nm2。
SEM morphology analysis uses Hitachi TM3000 type and HitachiSU8020 type desk type scanning electronic microscope.
The solid state nmr experiment of sample carries out on Bruker AvanceIII600 (14.1Tesla) spectrometer.29Si MAS NMR experiment uses 7mm double resonance probe, revolving speed 6kHz.Using high power proton-decoupled program, sampling number 5000- 6000, π/4 pulse width is 2.5 μ s, sampling delay 10s, with 4,4- dimethyl -4- propanesulfonate (DSS) for chemical potential Reference is moved, 0ppm is corrected to.
Embodiment 1:
The synthesis of cupric Cu-SAPO-34 sample as copper source.
Each feed molar ratio and crystallization condition are shown in Table 1, and specific blending process is as follows:
Boehmite (65 weight %), water, phosphoric acid (85 weight %), silica solution (31 are sequentially added into 2L synthesis reactor Weight %), Salzburg vitriol, tetraethylenepentamine (TEPA), optional organic formwork agent R1 and SAPO-34 crystal seed, stirring is equal It is even, it then seals, is warming up to 140-200 DEG C under stiring, crystallization 5-24h.Solid product is centrifuged, is washed with deionized water It washs sample and obtains stand-by Cu-SAPO-34 molecular sieve after 120 DEG C of air dryings to neutrality and (be named as Cu-34-x, x= a,b,c,d).It is the granularity in order to reduce the high-copper Cu-SAPO-34 of synthesis that crystal seed is added in synthesis, after participating in it preferably Continuous crystallization, plays the role of crystal seed and copper source, and the addition of crystal seed is also beneficial to improve product yield.Crystal seed is referenced patent The nanoscale SAPO-34 of CN104340986B synthesis.The XRD of four high-copper Cu-SAPO-34 samples of synthesis is shown in Fig. 1, sample The SEM of Cu-34-a is shown in Fig. 2, and granularity is in 300-500nm.
Feed molar ratio and crystallization condition of the table 1 as the cupric Cu-SAPO-34 of copper source
aInventory (wt%)=(M of crystal seedCrystal seed/(MP2O5+MAl2O3+MSiO2)) * 100%, product yield=(MProduct original powder* 85%/(MP2O5+MAl2O3+MSiO2) * 100%
Embodiment 2~9: the preparation of high hydrothermal stability Cu-SAPO-34 zeolite product
Each feed molar ratio and crystallization condition are shown in Table 2.Specific blending process is as follows:
First by silicon source and water mixed dissolution, optional phosphorus source, silicon source and template R are then successively added thereto.To The Cu-SAPO-34 sample prepared in embodiment 1 is added in said mixture.Gel is transferred to not after being stirred at room temperature uniformly In rust steel reaction kettle.After reaction kettle is put into baking oven, it is warming up to 160-200 DEG C of reaction 0.5-72h, crystallization terminates.By solid product Centrifugation, washing obtain molecular screen primary powder sample after drying in 120 DEG C of air.Sample does XRD analysis, and peak shape presents typical The XRD diffraction spectrogram of CHA structure characteristic peak, embodiment 3 is shown in Fig. 3.In addition, Fig. 4 gives the Cu-SAPO- prepared in embodiment 5 The SEM photograph of 34 molecular sieves.As can be seen that the pattern of gained sample is rhombohedron shape, particle size range is 1-2 μm.It can be seen that use The granularity that synthetic method of the present invention prepares sample is less than normal compared with the crystal size of conventional hydrothermal synthesis SAPO molecular sieve.This contains with using Copper Cu-SAPO-34 has direct relation as raw material and crystal seed.After sample is roasted removed template method, its specific surface area and hole are surveyed Hold, sample has high BET specific surface area 560.7m2g-1And big pore volume 0.29cm3g-1, wherein according to t-plot method The micropore specific area and micropore volume being calculated are respectively 542.5m2g-1And 0.25cm3g-1.Fig. 5 gives 7 sample of embodiment The solid state nmr of product29Si spectrogram, there is single peak in 90ppm respectively in sample as the result is shown, and the Si (4Al) for being attributed to sample matches Position environment.
Embodiment 10
By the sample of embodiment 3,5 and 8 in 650 DEG C of high-temperature roasting 2h, after removing template, it to be used for NH3Selective reduction Remove NOxThe catalytic performance test of reaction.Specific experiment process and condition are as follows: sample tabletting is sieved after roasting, weighs 0.1g 60 to 80 mesh samples are mixed with 0.4g quartz sand (60 to 80 mesh), are packed into fixed bed reactors.Lead to nitrogen activation at 600 DEG C Then 40min is cooled to 120 DEG C and starts to react, and is warming up to 550 DEG C.Reactor feed gas are as follows: NO:500ppm, NH3: 500ppm, O2: 5%, H2O:5%, N2As Balance Air, gas flow rate 300mL/min.Reaction end gas is using Bruker company 27 type instrument of Tensor, carries out online FTIR analysis, as a result sees Fig. 6.It can be seen that 3 sample of embodiment is due to lower Copper content, lower than 200 DEG C of temperature section activity it is lower, as temperature elevation of NO conversion ratio is stepped up, 500 DEG C still keep close 100% conversion ratio.5 sample copper content of embodiment improves, therefore improves its low-temperature reactivity, with temperature liter High NO conversion ratio further increases, 350 DEG C close to 100% conversion ratio, temperature is increased to after 450-500 DEG C, and conversion ratio omits There is decline, but remains at 90% or more.8 sample of embodiment has higher Cu content, and therefore, low temperature active is high, but partially High Cu content will lead to high temperature section side reaction generation, so that NO conversion ratio declines.
Embodiment 11
5 sample of embodiment is in 650 DEG C of high-temperature roasting 2h, after removing template, further in 800 DEG C of High-temperature water heat treatments 16 Hour, it is respectively designated as sample 5-H and then carries out NH3Selective reduction removes NOxThe catalytic performance test of reaction.Test condition With embodiment 10, Fig. 7 is as a result seen.It can be seen that sample its SCR reactivity after high temperature water process has all obtained preferable guarantor It holds, shows
There is excellent high-temperature hydrothermal stability with Cu-SAPO-34 prepared by methods described herein, have trend The condition of practical application, and the high-temperature sample hydrothermal stability of Cu too high levels is poor.
Embodiment 12
The synthesis process of cupric Cu-SAPO-42 sample as copper source is as follows:
Boehmite (65 weight %), water, phosphoric acid (85 weight %), silica solution (31 are sequentially added into 2L synthesis reactor Weight %), Salzburg vitriol, tetraethylenepentamine (TEPA), diethanol amine, trimethylamine (33 weight %), hydrofluoric acid (40 weights Measure %) and SAPO-42 crystal seed.Charge ratio Al2O3:P2O5:SiO2: Cu- tetraethylenepentamine complex compound: diethanol amine: trimethylamine: Hydrofluoric acid: H2O=1:1:1.0:0.10:3.0:0.9:0.5:50, crystal seed feed intake 10 weight %.It stirs evenly, then seals, 180 DEG C are warming up under stirring, crystallization 48h.Solid product is centrifuged, sample is washed with deionized to neutrality, at 120 DEG C After air drying, stand-by Cu-SAPO-42 molecular sieve, number Cu-42,9 weight % of copper content are obtained.The Cu- of synthesis The XRD of SAPO-42 sample is shown in Fig. 8.
Embodiment 13-14
Each feed molar ratio and crystallization condition are shown in Table 3.Specific blending process is as follows:
First by silicon source and water mixed dissolution, optional phosphorus source, silicon source are then successively added thereto.Diethanol amine, three Methylamine and hydrofluoric acid.The Cu-SAPO-42 sample prepared in embodiment 12 is added into said mixture.It is stirred at room temperature uniformly Gel is transferred in stainless steel cauldron afterwards.After reaction kettle is put into baking oven, 200 DEG C of reaction 48h are warming up to, crystallization terminates.It will Solid product centrifugation, washing obtain molecular screen primary powder sample after drying in 120 DEG C of air.Sample does XRD analysis, and peak shape is in The XRD diffraction spectrogram of now typical LTA structure characteristic peak, embodiment 13 is shown in Fig. 9.It is made in addition, Figure 10 gives in embodiment 14 The SEM photograph of standby Cu-SAPO-42 molecular sieve.
3 synthesis material molar ratio of table, crystallization condition and composite result
Comparative example 1-4:
Each feed molar ratio and crystallization condition are shown in Table 3.Specific step is as follows: sequentially adding into 100mL synthesis reactor quasi- Boehmite (65 weight %), water, phosphoric acid (85 weight %), silica solution (31 weight %), Salzburg vitriol, tetraethylenepentamine And diethylamine (DEA).SAPO-34 seed load is the 5wt% of reaction mixture solid content, stirs evenly, then seals, 170 DEG C, crystallization 3 days are warming up under stirring.Solid product is centrifuged.Sample is washed with deionized to neutrality, at 120 DEG C After air drying, Cu-SAPO-34 sieve sample is obtained.
4 feed molar ratio of table and crystallization condition
Product yield=(MProduct* 85%/(MP2O5+MAl2O3+MSiO2) * 100%
Figure 11 gives the SEM electromicroscopic photograph of comparative example 3, and the granularity of sample is at 5-10 microns as the result is shown.Figure 12 Give comparative example 329Si NMR solid state nmr spectrogram, it is found that in addition to Si (4Al) signal, sample is in 110ppm There are apparent signals, belong to Si (0Al).Copper-amine complex template is easy to that silicon island is caused to be formed.From four comparative examples As a result it is found that for using copper-amine complex and other organic amines to be total to for templated synthesis Cu-SAPO-34 molecular sieve, copper is reduced The inventory of amine complex can reduce the copper content in product.But the copper content of synthesized product is also controlled by conjunction simultaneously Silica inventory in architectonical.When the inventory of silica reduces, the copper content in product declines limitation.Silica It is reduced simultaneously with the inventory of copper-amine complex, the crystallization rate for also resulting in SAPO molecular sieve slows down, and yield is decreased obviously (right Ratio 4).
Method provided by the invention solves the above problem.The Cu-SAPO Molecular sieve raw material of high copper content prefabricated first is closed It is higher at the copper-amine complex amount put into the process, improve crystallization rate and product yield.Then, by prefabricated Cu-SAPO-34 Raw material carries out the synthesis of Cu-SAPO-34 as copper source, part silicon phosphorus aluminium original and crystal seed.It walks in synthesis process herein, avoids copper The problem of amine complex and other organic amine templates compete, product silicone content and silicon atom distribution are controlled by having for selection substantially Machine amine template.Cu content can also regulate and control in relatively wide range, realize the controlledly synthesis of Cu-SAPO-34.Cu-SAPO Silicon amount and coordination environment in molecular sieve improve to improve the hydrothermal stability of the Cu-SAPO-34 of synthesis and provide possibility.
Comparative example 5
The sample that comparative example 1-4 is obtained is in 650 DEG C of high-temperature roasting 2h, after removing template, further in 800 DEG C of high temperature Hydro-thermal process 16 hours, the diffraction maximum that XRD test three samples of display belong to CHA crystal phase disappeared, and sample is within the scope of 20-25 degree There is diffraction maximum, forms dense phase, it is seen that its high-temperature hydrothermal stability is poor.
It should be pointed out that the professional technician for making the art, without departing from the principle of the present invention, energy Enough realize various modifications to these embodiments, and these modifications also should be regarded as within the scope of the present invention.

Claims (14)

1. a kind of method for preparing Cu-SAPO molecular sieve, which is characterized in that the described method comprises the following steps:
(1) using the Cu-SAPO molecular sieve of the template synthesis high copper content comprising copper-amine complex, Cu load capacity is 5- 20wt%；
(2) organic amine template R and water and optional silicon source, silicon source and phosphorus source are mixed to prepare crystallization liquid；
(3) using the Cu-SAPO molecular sieve of high copper content obtained in step (1) as crystallization obtained in raw material and step (2) Liquid mixes and carries out hydrothermal crystallizing, obtains Cu-SAPO zeolite product.
2. according to the method for claim 1, which is characterized in that the Cu-SAPO molecular sieve of high copper content in the step (1) It is that copper-amine complex is used to be mixed into total template as single template or with organic amine template R1, by silicon source, silicon source, phosphorus source The Cu-SAPO synthesized with water by hydrothermal crystallizing, the organic amine template R1 are selected from triethylamine, diethylamine, morpholine, tetraethyl The mixing of one or more of ammonium hydroxide, propylamine and piperazine.
3. according to the method for claim 1, which is characterized in that the copper-amine complex in the step (1) includes the more second of copper- Alkene polyamines complex compound, preferably Cu- tetraethylenepentamine complex compound, Cu- triethylene tetramine complex compound, Cu- diethylenetriamine complex compound With Cu- pentaethylene hexamine complex compound.
4. according to the method for claim 2, which is characterized in that the Cu-SAPO molecular sieve of high copper content in the step (1) Synthesis carried out in the presence of SAPO crystal seed.
5. according to the method for claim 1, which is characterized in that silicon source used in the step (2) is selected from positive silicic acid second One or more of ester, silica solution and white carbon black；Silicon source is selected from aluminium isopropoxide, boehmite, Aluminum sol and aluminium hydroxide One or more of；Phosphorus source is selected from one or more of phosphoric acid, phosphorous acid and phosphorus pentoxide；Organic amine template R choosing From the mixing of one or more of triethylamine, diethylamine, morpholine, tetraethyl ammonium hydroxide, propylamine and piperazine.
6. according to the method for claim 1, which is characterized in that silicon source used in the step (2), silicon source, has phosphorus source The molar ratio of machine amine template R and water is Al2O3:P2O5:SiO2:R:H2O=1:0.5~2:0.01~1.5:0.5~10:15 ~200, preferably Al2O3:P2O5:SiO2:R:H2O=1:0.7~1.5:0.1~1.0:1~5:30~100.
7. according to the method for claim 1, which is characterized in that the Cu-SAPO raw material of high copper content described in step (3) Inventory be prepare crystallization liquid in solid oxidation amount of substance summation 2-200wt%.
8. according to the method for claim 1, which is characterized in that the temperature of progress hydrothermal crystallizing is in the step (3) 140-240 DEG C, the time is 0.5~72 hour；Preferred crystallization temperature is 150-200 DEG C.
9. according to the method for claim 1, which is characterized in that the Cu of the Cu-SAPO zeolite product prepared in step (3) Load capacity is the 10-70% of the copper content of the Cu-SAPO raw material of high copper content.
10. according to method of any of claims 1-9, which is characterized in that the Cu-SAPO molecular sieve includes Cu- SAPO-34 molecular sieve, any one of Cu-SAPO-42 molecular sieve, Cu-DNL-6 (RHO).
11. a kind of Cu-SAPO molecular screen primary powder, is synthesized by method according to claim 1 to 10.
12. Cu-SAPO molecular screen primary powder according to claim 11, which is characterized in that the Cu-SAPO molecular sieve is Cu-SAPO-34 molecular sieve, the Cu-SAPO-34 molecular sieve are rhombohedron shape, and preferable particle size range is 1-2 μm.
13. one kind is used for NOxThe catalyst of selective reduction elimination reaction, by according to claim 1 to 10 The molecular sieve of method synthesis is obtained through roasting in 500~800 DEG C of air.
14. a kind of method for improving Cu-SAPO molecular sieve high-temperature hydrothermal stability, which is characterized in that the described method includes: It goes forward side by side being mixed by using the Cu-SAPO molecular sieve of the high copper content of the template synthesis comprising copper-amine complex with crystallization liquid Row hydrothermal crystallizing, wherein the crystallization liquid is by mixing organic amine template R and water and optional silicon source, silicon source and phosphorus source Prepared by conjunction.
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