CN108905603A - The preparation method and product and purposes of CuCeSAPO-34 molecular sieve - Google Patents

The preparation method and product and purposes of CuCeSAPO-34 molecular sieve Download PDF

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CN108905603A
CN108905603A CN201810572583.3A CN201810572583A CN108905603A CN 108905603 A CN108905603 A CN 108905603A CN 201810572583 A CN201810572583 A CN 201810572583A CN 108905603 A CN108905603 A CN 108905603A
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cucesapo
molecular sieve
preparation
cerium salt
crystallization
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陈建军
高向平
李俊华
张亚青
赵新红
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Yancheng Environmental Engineering Technology Research And Development Center Tsinghua University
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Yancheng Environmental Engineering Technology Research And Development Center Tsinghua University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates (SAPO compounds)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst

Abstract

The preparation method and product and purposes of CuCeSAPO-34 molecular sieve of the present invention, tetraethyl ammonium hydroxide is added in deionized water and is stirred, after solution is uniform, addition aluminium isopropoxide is to being completely dissolved, then orthophosphoric acid and ethyl orthosilicate is added, cerium salt is added after mixing, mantoquita is added after being sufficiently stirred, complete colloidal sol will then be stirred and be fitted into crystallization in hydrothermal reaction kettle, then room temperature is cooling, and solid crystallized product is separated with mother liquor, washing to neutrality, after roasting in dry and air, CuCeSAPO-34 molecular sieve catalyst is obtained.Preparation method of CuCeSAPO-34 molecular sieve catalyst provided by the invention and products thereof and purposes, introduce copper, cerium etc., without subsequent ion exchange step, utilize the synergistic effect of copper, cerium between the two, the load capacity that input amount by controlling cerium salt adjusts cerium obtains the molecular sieve catalyst of different catalytically active, better crystallinity degree, synthesis step are simple.

Description

The preparation method and product and purposes of CuCeSAPO-34 molecular sieve
Technical field
The invention belongs to molecular sieve preparation fields, and in particular to the preparation method and product of CuCeSAPO-34 molecular sieve and Purposes.
Background technique
With NH3For reducing agent Selective Catalytic Reduction of NOxThat is NH3SCR technology has during catalytic elimination NOx Particularly important effect, key core are the exploitations of SCR catalyst system.
Nitrogen oxides（NOx）, main source is moving source（Motor vehicle accounts for about 49%）And stationary source（Thermal power plant, Industrial Boiler accounts for about 46%）, serious pollution is caused to ecological environment and living environment.Industrial applications are more mature at present Gas denitrifying technology be using vanadium titanium system as the NH of dominant catalyst3- SCR technology, V2O5-WO3-TiO2Although catalyst is For many years, but there are still some the shortcomings that itself can not overcoming for industrial application, for example, operation temperature window is relatively narrow, high temperature when N2O is big Amount generates and causes N2Generate selectivity decline, SO2To SO3Aoxidize serious and active component V2O5With bio-toxicity, endanger people Body health etc..In addition, denitration reaction needs to be additionally provided energy, the significant wastage of the energy is caused.But if in middle low temperature item Denitration may be implemented under part, so that it may improve the utilization efficiency of the energy, therefore, exploitation has the catalysis of middle low-temperature denitration, non-vanadium NH3SCR catalyst system becomes scientific research personnel and NOxThe hot spot of emission control worker research.
Small pore molecular sieve CuSAPO-34 has superior denitration catalyst performance, and aperture is small, has to the catalysis of nitrogen oxides Preferable selectivity, large specific surface area improve the conversion ratio of catalysis, and hydrothermal stability is high, overcome harsh reaction condition, However its synthesis cost is higher, limits the application of molecular sieve, while the content of Cu and form have seriously affected urging for material Change performance, if the method for exploring the material of inexpensive synthesized high-performance, application value will more extensively.
Summary of the invention
Goal of the invention：To solve problems of the prior art, the present invention provides a kind of CuCeSAPO-34 molecular sieve Preparation method and product and purposes.
To achieve the above object, the technical solution adopted by the present invention is：
The preparation method of CuCeSAPO-34 molecular sieve, includes the following steps：
Step 1: by tetraethyl ammonium hydroxide be added deionized water in be stirred, it is to be mixed uniformly after, addition aluminium isopropoxide extremely It is completely dissolved, orthophosphoric acid and ethyl orthosilicate is then added, cerium salt is added after mixing, mantoquita is added after being sufficiently stirred, stir Uniformly, colloidal sol is obtained；
Step 2: the colloidal sol in step 1 is fitted into crystallization in hydrothermal reaction kettle, room temperature is cooling after the completion of crystallization, will consolidate Body crystallized product is separated with mother liquor, and solid crystallized product is washed with deionized to neutrality, then drying roasts in air, With the CuCeSAPO-34 molecular sieve of catalytic activity needed for obtaining；
Input amount by controlling cerium salt adjusts the load capacity of cerium, and obtains different catalytically active according to step 2 CuCeSAPO-34 molecular sieve, in this method, the molar ratio for controlling cerium salt is 0-0.06.
Further, the aluminium isopropoxide, orthophosphoric acid, ethyl orthosilicate, deionized water, tetraethyl ammonium hydroxide, mantoquita, The molar ratio 1 of each component when the additive amount of cerium salt should make crystallization:1.2:0. 6: 70:2:0-0.06:0-0.06.
Further, in this method, aluminium isopropoxide, orthophosphoric acid, ethyl orthosilicate, deionized water, tetraethyl hydrogen-oxygen are controlled Change ammonium, mantoquita, cerium salt each component of additive amount when should make crystallization molar ratio 1:1.2:0. 6: 70:2: 0.02: 0.02。
Further, in step 1, the cerium salt is cerous nitrate, and mantoquita is copper acetate.
Further, in step 2, the temperature of crystallization is 150-200 DEG C, crystallization time 8-72h.
Further, in step 2, drying temperature is 80-120 DEG C, drying time 6-18h.
Further, in step 2, maturing temperature is 500-800 DEG C, calcining time 3-8h, the heating in roasting process Rate is 0. 5-10 DEG C/min.
Further, CuCeSAPO-34 molecular sieve made from the preparation method of CuCeSAPO-34 molecular sieve catalyst.
Further, it is used for NH3- SCR reaction.
Compared with prior art, beneficial effects of the present invention are：
The invention discloses the preparation method of CuCeSAPO-34 molecular sieve and product and purposes will using a step hydrothermal synthesis method Tetraethyl ammonium hydroxide is added in deionized water and is stirred, and after solution is uniform, adds aluminium isopropoxide to being completely dissolved, then Orthophosphoric acid and ethyl orthosilicate is added, the cerium salt that molar ratio is 0-0.06 is added after mixing, mantoquita is added after being sufficiently stirred, with After will stir complete colloidal sol and be fitted into crystallization in hydrothermal reaction kettle, then room temperature is cooling, solid crystallized product is separated with mother liquor, Washing obtains CuCeSAPO-34 molecular sieve, can be used for NH to neutrality after roasting in dry and air3- SCR reaction.This hair The preparation method and product and purposes of the CuCeSAPO-34 molecular sieve of bright offer, introduce copper, cerium isoreactivity species, and cerium salt adds The CHA structure for entering not influence CuSAPO-34 molecular sieve, can effectively reduce Cu0Production quantity, weaken NH3Non-oxide reduction it is anti- It answers, the addition of Ce can also stabilizing active species Cu+, it is simple and easy to control, it is not necessarily to subsequent ion exchange step, using a kind of ammonium salt, The waste that not will cause amine, using the synergistic effect of copper, cerium between the two, the input amount by controlling cerium salt adjusts the load of cerium Amount, obtains having different NH3The molecular sieve of-SCR catalytic activity, moreover it is possible to obtain NH3- SCR catalytic activity and water-resistance are excellent CuCeSAPO-34 molecular sieve, compared to existing CuSAPO-34 molecular sieve, CuCeSAPO-34 molecular sieve of the invention has excellent Different catalytic activity, crystallinity is preferable, and for crystal less than 1 μm, pattern is uniform, and preparation method only relates to the mixing of primary raw materials, The CuCeSAPO-34 molecular sieve that different content can be synthesized can also synthesize without containing transition metal hetero-atom or contain only one The molecular sieve of kind transition metal hetero-atom, synthesis step is simple compared with conventional method, there is huge prospects for commercial application.
Detailed description of the invention
Fig. 1 is XRD spectra of the invention；
Fig. 2 is that the SEM of magnification at high multiple of the invention schemes；
Fig. 3 is the SEM figure that low power of the invention is amplified；
Fig. 4 is nitrogen adsorption isotherm of the invention.
Specific embodiment
The following describes the present invention in detail with reference to examples.
As shown in Figs 1-4, the preparation method of CuCeSAPO-34 molecular sieve is prepared using a step hydrothermal synthesis method CuCeSAPO-34 molecular sieve is simultaneously used for NH3- SCR reaction, includes the following steps：
It is stirred Step 1: tetraethyl ammonium hydroxide is added in deionized water, after mixing evenly to solution, adds isopropanol Then aluminium is added orthophosphoric acid and ethyl orthosilicate, cerium salt is added after mixing, mantoquita is added after being sufficiently stirred to being completely dissolved, It stirs evenly, obtains colloidal sol；
Step 2: the colloidal sol in step 1 is fitted into crystallization in hydrothermal reaction kettle, room temperature is cooling after the completion of crystallization, will consolidate Body crystallized product is separated with mother liquor, and solid crystallized product is washed with deionized and obtains after roasting in drying, air to neutrality To required CuCeSAPO-34 molecular sieve.
In this method, control aluminium isopropoxide, orthophosphoric acid, ethyl orthosilicate, deionized water, tetraethyl ammonium hydroxide, mantoquita, The molar ratio 1 of each component when the additive amount of cerium salt should make crystallization:1.2:0. 6: 70:2:0-0.06:0-0.06.
Preferably, aluminium isopropoxide, orthophosphoric acid, ethyl orthosilicate, deionized water, tetraethyl ammonium hydroxide, mantoquita, cerium salt The molar ratio 1 of each component when additive amount should make crystallization:1.2:0. 6: 70:2: 0.03:0.03.
Preferably, aluminium isopropoxide, orthophosphoric acid, ethyl orthosilicate, deionized water, tetraethyl ammonium hydroxide, mantoquita, cerium salt The molar ratio 1 of each component when additive amount should make crystallization:1.2:0. 6: 70:2: 0.02:0.02.
In step 1, the present invention prepares CuCeSAPO-34 molecular sieve using a step hydrothermal synthesis method, and passes through control cerium salt Input amount adjust cerium load capacity, obtain the CuCeSAPO-34 molecular sieve catalyst of different catalytically active according to step 2, into One step obtains NH by controlling the input amount of cerium salt3The CuCeSAPO-34 molecular sieve that-SCR catalytic activity is had excellent performance.
In step 1, cerium salt is cerous nitrate, and mantoquita is copper acetate.
In step 2, the temperature of crystallization is 150-200 DEG C, preferably 170 DEG C, crystallization time 8-72h, preferably 72h.
In step 2, drying temperature is 80-120 DEG C, and drying time 6-18h, preferably drying temperature are 80 DEG C, when dry Between be 12h.
In step 2, maturing temperature be 500-800 DEG C, preferably 550 DEG C, calcining time 3-8h, preferably 5h, roasting process In heating rate be 0. 5-10 DEG C/min, preferably 3 DEG C/min.
Embodiment 1
CuCeSAPO-34 molecular sieve is prepared using a step hydrothermal synthesis method and is used for NH3- SCR reaction, CuCeSAPO-34 molecule The preparation method of sieve, includes the following steps：
1.47g tetraethyl ammonium hydroxide is added in 6.3g deionized water and is stirred, after solution is uniform, addition 2.08g is different Then 1.38g orthophosphoric acid and 0.63g ethyl orthosilicate is added to being completely dissolved in aluminium propoxide, 0.08g nitric acid is added after mixing Cerium is added 0.03g copper acetate, will then stir complete colloidal sol and be fitted into crystallization in hydrothermal reaction kettle, then room after being sufficiently stirred Temperature is cooling, and solid crystallized product is separated with mother liquor, and washing to neutrality obtains molecular sieve powder after 80 DEG C of air dryings, Molecular screen primary powder is roasted into 5h in 550 DEG C of air, finally obtains CuCeSAPO-34 molecular sieve catalyst.
Fig. 1 is the XRD characterization result of CuCeSAPO-34 zeolite product, it can be seen that product is typical CuCeSAPO- 34 structures, and there is preferable crystallinity, Fig. 2 and Fig. 3 are SEM stereoscan photograph of the product in different amplification, Can will become apparent from CuCeSAPO-34 zeolite product is pure phase, and less than 1 μm, pattern is uniform, is extraordinary nanoscale molecular Material is sieved, Fig. 4 is the nitrogen adsorption isotherm of product, in the relative pressure 0.4 of initial point<P/P0<When 1, there is hysteresis in centre Ring shows that product is a kind of multistage porous molecular sieve.
Embodiment 2
The raw materials sequence and milling time for preparing CuCeSAPO-34 molecular sieve are the same as embodiment 1, wherein aluminium isopropoxide, positive phosphorus Acid, ethyl orthosilicate, deionized water, tetraethyl ammonium hydroxide, mantoquita, cerium salt each component of additive amount when should make crystallization A12O3、P2O5、SiO2、H2O, TEAOH, mantoquita, cerium salt molar ratio be 1:1.2:0. 6: 70:2: 0.01:0, stirring is complete Colloidal sol be fitted into hydrothermal reaction kettle, in 170 DEG C of crystallization 3d, then room temperature is cooling, and solid crystallized product is separated with mother liquor, is washed It washs to neutrality, and dry at 80 DEG C, roasts 5h in 550 DEG C of air, finally obtain CuCeSAPO-34 molecular sieve, inorganic original Sub- utilization rate is 85.5%.
Embodiment 3
Preparation method, charging sequence and the milling time of CuCeSAPO-34 zeolite product are the same as embodiment 1, wherein isopropanol Aluminium, orthophosphoric acid, ethyl orthosilicate, deionized water, tetraethyl ammonium hydroxide, mantoquita, cerium salt additive amount when should make crystallization Each component A12O3、P2O5、SiO2、H2O, TEAOH, mantoquita, cerium salt molar ratio be 1:1.2:0. 6: 70:2: 0.01:0, Complete colloidal sol is stirred to be fitted into hydrothermal reaction kettle, in 170 DEG C of crystallization 3d, after the reaction was completed, the product deionization that will be obtained Water sufficiently washs, and dry at 80 DEG C, obtains CuCeSAPO-34 molecular sieve after air roasting after.
Embodiment 4
Preparation method, charging sequence and the milling time of CuCeSAPO-34 molecular sieve with embodiment 1, aluminium isopropoxide, orthophosphoric acid, Ethyl orthosilicate, deionized water, tetraethyl ammonium hydroxide, mantoquita, cerium salt each component of additive amount when should make crystallization A12O3、P2O5、SiO2、H2O, TEAOH, mantoquita, cerium salt molar ratio be 1:1.2:0. 6: 70:2:0.06:0, in 170 DEG C of crystalline substances Change 3d after the reaction was completed sufficiently to wash obtained product with deionized water, and dry at 80 DEG C, through air roasting after After obtain CuCeSAPO-34 molecular sieve.
Embodiment 5
Preparation method, charging sequence and the milling time of CuCeSAPO-34 molecular sieve with embodiment 1, aluminium isopropoxide, orthophosphoric acid, Ethyl orthosilicate, deionized water, tetraethyl ammonium hydroxide, mantoquita, cerium salt each component of additive amount when should make crystallization A12O3、P2O5、SiO2、H2O, TEAOH, mantoquita, cerium salt molar ratio be 1:1.2:0. 6: 70:2:0.01:0.01, in 170 DEG C Crystallization 3d.After the reaction was completed, obtained product is sufficiently washed, and dry at 80 DEG C with deionized water, is roasted after through air CuCeSAPO-34 molecular sieve is obtained after burning.
Embodiment 6
Preparation method, charging sequence and the milling time of CuCeSAPO-34 molecular sieve with embodiment 1, aluminium isopropoxide, orthophosphoric acid, Ethyl orthosilicate, deionized water, tetraethyl ammonium hydroxide, mantoquita, cerium salt each component of additive amount when should make crystallization A12O3、P2O5、SiO2、H2O, TEAOH, mantoquita, cerium salt molar ratio be 1:1.2:0. 6: 70:2:0.005:0.01, in 170 DEG C crystallization 3d.After the reaction was completed, obtained product is sufficiently washed with deionized water, and dry at 80 DEG C, through air after CuCeSAPO-34 molecular sieve is obtained after roasting.
Embodiment 7
Preparation method, charging sequence and the milling time of CuCeSAPO-34 molecular sieve with embodiment 1, aluminium isopropoxide, orthophosphoric acid, Ethyl orthosilicate, deionized water, tetraethyl ammonium hydroxide, mantoquita, cerium salt each component of additive amount when should make crystallization A12O3、P2O5、SiO2、H2O, TEAOH, mantoquita, cerium salt molar ratio be 1:1.2:0. 6: 70:2:0.01:0.02, in 170 DEG C crystallization 3d.After the reaction was completed, obtained product is sufficiently washed with deionized water, and dry at 80 DEG C, through air after CuCeSAPO-34 molecular sieve is obtained after roasting.
Embodiment 8
Preparation method, charging sequence and the milling time of CuCeSAPO-34 zeolite product are the same as embodiment 1, aluminium isopropoxide, positive phosphorus Acid, ethyl orthosilicate, deionized water, tetraethyl ammonium hydroxide, mantoquita, cerium salt each component of additive amount when should make crystallization A12O3、P2O5、SiO2、H2O, TEAOH, mantoquita, cerium salt molar ratio be 1:1.2:0. 6: 70:2:0.02:0.02, in 170 DEG C crystallization 3d.After the reaction was completed, obtained product is sufficiently washed with deionized water, and dry at 80 DEG C, through air after CuCeSAPO-34 molecular sieve is obtained after roasting.
Embodiment 9
Preparation method, charging sequence and the milling time of CuCeSAPO-34 molecular sieve with embodiment 1, aluminium isopropoxide, orthophosphoric acid, Ethyl orthosilicate, deionized water, tetraethyl ammonium hydroxide, mantoquita, cerium salt each component of additive amount when should make crystallization A12O3、P2O5、SiO2、H2O, TEAOH, mantoquita, cerium salt molar ratio be 1:1.2:0. 6: 70:2:0:0.06, in 170 DEG C of crystalline substances Change 3d.After the reaction was completed, obtained product is sufficiently washed with deionized water, and dry at 80 DEG C, through air roasting after After obtain CuCeSAPO-34 molecular sieve.
Embodiment 10
Preparation method, charging sequence and the milling time of CuCeSAPO-34 molecular sieve with embodiment 1, aluminium isopropoxide, orthophosphoric acid, Ethyl orthosilicate, deionized water, tetraethyl ammonium hydroxide, mantoquita, cerium salt each component of additive amount when should make crystallization A12O3、P2O5、SiO2、H2O, TEAOH, mantoquita, cerium salt molar ratio be 1:1.2:0. 6: 70:2:0.06:0.006, in 170 DEG C crystallization 3d.After the reaction was completed, obtained product is sufficiently washed with deionized water, and dry at 80 DEG C, through air after CuCeSAPO-34 molecular sieve is obtained after roasting.
The above is only a preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (9)

  1. The preparation method of 1.CuCeSAPO-34 molecular sieve, which is characterized in that include the following steps：
    Step 1: by tetraethyl ammonium hydroxide be added deionized water in be stirred, it is to be mixed uniformly after, addition aluminium isopropoxide extremely It is completely dissolved, orthophosphoric acid and ethyl orthosilicate is then added, cerium salt is added after mixing, mantoquita is added after being sufficiently stirred, stir Uniformly, colloidal sol is obtained；
    Step 2: the colloidal sol in step 1 is fitted into crystallization in hydrothermal reaction kettle, room temperature is cooling after the completion of crystallization, will consolidate Body crystallized product is separated with mother liquor, and solid crystallized product is washed with deionized to neutrality, roasts, obtains in air after dry Required CuCeSAPO-34 molecular sieve；
    In step 1, the input amount by controlling cerium salt adjusts the load capacity of cerium, and obtains different catalytically active according to step 2 CuCeSAPO-34 molecular sieve, in this method, the molar ratio for controlling cerium salt is 0-0.06.
  2. 2. the preparation method of CuCeSAPO-34 molecular sieve according to claim 1, which is characterized in that the aluminium isopropoxide, Orthophosphoric acid, ethyl orthosilicate, deionized water, tetraethyl ammonium hydroxide, mantoquita, the additive amount of cerium salt are each when should make crystallization The molar ratio of component is 1:1.2:0. 6: 70:2:0-0.06：0-0.06.
  3. 3. the preparation method of CuCeSAPO-34 molecular sieve according to claim 2, which is characterized in that the aluminium isopropoxide, Orthophosphoric acid, ethyl orthosilicate, deionized water, tetraethyl ammonium hydroxide, mantoquita, the additive amount of cerium salt are each when should make crystallization The molar ratio of component is 1:1.2:0. 6: 70:2: 0.02:0.02.
  4. 4. the preparation method of CuCeSAPO-34 molecular sieve according to claim 1, which is characterized in that described in step 1 Cerium salt is cerous nitrate, and mantoquita is copper acetate.
  5. 5. the preparation method of CuCeSAPO-34 molecular sieve according to claim 1, which is characterized in that in step 2, crystallization The temperature of reaction is 150-200 DEG C, crystallization time 24-72h.
  6. 6. the preparation method of CuCeSAPO-34 molecular sieve according to claim 1, which is characterized in that dry in step 2 Temperature is 80-120 DEG C, drying time 6-18h.
  7. 7. the preparation method of CuCeSAPO-34 molecular sieve according to claim 1, which is characterized in that in step 2, roasting Temperature is 500-800 DEG C, calcining time 3-8h, and the heating rate in roasting process is 0. 5-10 DEG C/min.
  8. 8. CuCeSAPO- made from a kind of preparation method of -7 any CuCeSAPO-34 molecular sieves according to claim 1 34 molecular sieves.
  9. 9. a kind of application of CuCeSAPO-34 molecular sieve according to claim 8, which is characterized in that be used for NH3- SCR is anti- It answers.
CN201810572583.3A 2018-06-06 2018-06-06 The preparation method and product and purposes of CuCeSAPO-34 molecular sieve Pending CN108905603A (en)

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CN104888851A (en) * 2015-06-03 2015-09-09 中国科学院生态环境研究中心 CuCe-SAPO-34 molecular sieve catalyst, as well as preparation method and use thereof
CN105749965A (en) * 2014-09-09 2016-07-13 天津大学 Metal-cerium-doped Cu-SAPO-34 catalyst and method for preparing same
US20180021764A1 (en) * 2013-03-13 2018-01-25 Basf Corporation Stabilized metal-exchanged sapo material

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CN104340986A (en) * 2013-07-30 2015-02-11 中国科学院大连化学物理研究所 Method for preparing small granulated SAPO-34 molecular sieve, product prepared through method, and use of product
CN103641131A (en) * 2013-12-10 2014-03-19 吉林大学 Slice-shaped nanometer SAPO-34 molecular sieve with relatively low silicon content, preparation method and application thereof
CN105749965A (en) * 2014-09-09 2016-07-13 天津大学 Metal-cerium-doped Cu-SAPO-34 catalyst and method for preparing same
CN104888851A (en) * 2015-06-03 2015-09-09 中国科学院生态环境研究中心 CuCe-SAPO-34 molecular sieve catalyst, as well as preparation method and use thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3939937A1 (en) 2020-07-13 2022-01-19 Baotou Research Institute of Rare Earths Molecular sieve and its preparation method
US11590480B2 (en) 2020-07-13 2023-02-28 Baotou Research Institute of Rare Earths Molecular sieve and its preparation method

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