CN117160529A - Cu-based SAPO-17 monolithic catalyst, and preparation method and application thereof - Google Patents
Cu-based SAPO-17 monolithic catalyst, and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 45
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims abstract description 45
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- 238000006243 chemical reaction Methods 0.000 claims description 30
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 17
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- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
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- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 7
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 7
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- 239000007788 liquid Substances 0.000 claims description 4
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
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- 239000002808 molecular sieve Substances 0.000 abstract description 40
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 40
- 230000003197 catalytic effect Effects 0.000 abstract description 26
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- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract description 4
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
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- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a Cu-based SAPO-17 monolithic catalyst, a preparation method and application thereof, relates to the technical field of preparation and application of molecular sieve-based monolithic catalysts, and particularly relates to a monolithic catalyst which is pure in phase and has high denitration performance, and is prepared on a cheap cordierite support body through isomorphic silicon-aluminum ERI seed crystal induction and improved simple single-pot hydrothermal method. The method can be used for doping Cu species into a molecular sieve framework as an active component in a hydrothermal process, so that the problems of limited active sites and low loading capacity of the catalyst are avoided. Application of the catalyst to ammonia selective catalytic reduction of NO x The denitration efficiency can reach more than 90% in the temperature range of 200-500 ℃, and has excellent H resistance 2 O and SO resistance 2 Performance. The preparation method has simple process and low cost, and is suitable for catalytic denitration of various environments such as coke oven gas, diesel engine tail gas and the like.
Description
Technical Field
The invention relates to the technical field of preparation and application of molecular sieve-based monolithic catalyst materials, in particular to a Cu-based SAPO-17 monolithic catalyst, and a preparation method and application thereof.
Background
Ammonia selective catalytic reduction (NH 3 -SCR) technology is currently NO x The main stream means of elimination. The small-aperture molecular sieve catalyst has good hydrothermal stability, low-temperature catalytic activity and wider active temperature conversion window, so that the catalyst shows excellent NO in the denitration process x Catalytic efficiency, thus becoming NH with great potential 3 -SCR catalytic material.
The SAPO-17 is a phosphorus-aluminum molecular sieve with an Erionite (ERI) topological structure, and a four-membered ring and a double six-membered ring are connected together to form a three-dimensional eight-membered ring elliptic channel structure, the average effective pore size is 0.36nm, and the average effective pore size is close to a commercial out-of-stock catalytic material SSZ-13 molecular sieve (0.38 nm) of the same class of micropores. Typically, SAPO-17 is prepared by hydrothermal synthesis in an organic template system containing small cyclic amines such as piperidine, cyclohexylamine, quinuclidine, and the like, and often mesophase formation during synthesis. Lohse et al (Zeolite, 13 (1993) 549) and Zhou Rongfei (J Member Sci,520 (2016) 507) et al demonstrate the susceptibility of target products to the formation of hetero-crystalline phases such as SAPO-5 (AFI), SAPO-35 (LEV), SAPO-34 (CHA). Meanwhile, the period of the SAPO-17 synthesis is longer. Thus, the harsh synthesis conditions of SAPO-17 make the relevant literature reports rare. In addition, these documents report that SAPO-17 molecular sieves are mainly focused on being widely applied as catalysts, adsorbents, and membrane materials in the fields of industrial catalysis, adsorption, and separation such as methanol to light olefins (MTO), and gas separation. Froment et al (Res Financial Mark,9 (1992) 1) found that SAPO-17 had a mild natureAcid centers suitable for catalyzing the conversion of methanol to light olefins. Xu Jun (Tianjin chemical industry, 30 (2016) 17) and Liu Songlin (petrochemical industry, 51 (2022) 1263) and the like examine the influence of silicon-aluminum ratio on the morphology and acid property of the SAPO-17 molecular sieve, and MTO test shows that the SAPO-17 has excellent catalytic performance and potential commercial applicationThe application value. Zhou Rongfei et al (Micropor Mesopor Mater,263 (2018) 11) obtained AlPO-17 and SAPO-17 membranes by seed induction, and found that the prepared membranes were resistant to CO 2 /CH 4 And CO 2 /N 2 Exhibits higher CO separation 2 Permeability and selectivity. However, for NH 3 There are few reports on the study of SAPO-17 molecular sieves in SCR reactions.
Recently, zhu et al (J Catal,391 (2020) 346) reported rapid synthesis of high-silicon ERI-type molecular sieves (silica-alumina type) of the same configuration as SAPO-17 at high temperature, incorporating copper ions into the molecular sieves by ion exchange, the Cu-ERI molecular sieves being NH 3 SCR shows very high activity, even comparable to Cu-SSZ-13 catalytic performance. Although the introduction of Cu active species into a molecular sieve in an ion exchange mode is the most common method, the active sites of the catalyst obtained in the mode are unevenly distributed, the loading capacity is low, the process steps are complicated, the catalytic activity of the catalyst is low, and the application limitation is large. Then, developing a simple and efficient preparation method of the Cu-SAPO-17 denitration catalytic material is a key problem to be solved urgently.
To improve NH 3 Catalytic activity of SCR catalysts researchers have enhanced the ability of copper species to be reduced by modulating copper species loading, placements in the molecular sieve framework, and dispersibility. Ren et al (Chem Commun,47 (2011) 9789) designed a low-cost, nontoxic, harmless and readily available copper amine complex (Cu-TEPA) as a novel template for one-step hydrothermal synthesis of Cu-SSZ-13 molecular sieve catalyst. Compared with the traditional ion exchange mode, the Cu-TEPA serving as the template agent not only greatly reduces the preparation cost of the catalyst, but also provides a large amount of active copper species, and the prepared catalyst has high copper species content, good dispersion and excellent denitration performance. On the basis, zhong Zhaoxiang (Chem Eng J,420 (2021) 130425) synthesizes the Cu-SAPO-34/SiC integral catalytic membrane by adopting a one-pot method, solves the problem of load metal dispersibility, and can realize the purposes of removing NO and dedusting. In light of this, the development of novel monolithic catalysts is an effective approach to solving the above problems. Integral NH 3 SCR catalysts are not reported very often, typically by means of a coatingThe active component is covered on the carrier in a coating or dipping mode (Appl catalyst B: environ,187 (2016) 419), and the bonding force between the active layer and the carrier is weak; the existing monolithic catalyst has the reaction temperature of more than 200 ℃ and is stably applied to low-temperature NH 3 Further investigation is required in SCR. Then, it is critical to solve the above problems that a copper-based molecular sieve film having catalytic performance is grown on the surface of the carrier. Generally, the seed layer induction synthesis method can obtain a molecular sieve membrane with high crystallinity and high purity. Silicon aluminum type ERI molecular sieves (Mater Lett,260 (2020) 126934 and chinese patent invention ZL 201910036344.0) have been successfully obtained in our earlier work, so hydrothermal synthesis of copper-based SAPO-17 molecular sieve membrane catalysts on cordierite supports by means of seed induction is a simple and readily available route.
Disclosure of Invention
The invention aims to at least solve one of the technical problems existing in the prior art and provides a method for high-efficiency NH 3 -SCR denitration molecular sieve based monolithic catalyst and method of preparing the same.
The technical scheme of the invention is as follows:
the preparation method of the Cu-based SAPO-17 monolithic catalyst comprises the following steps:
s1: dissolving aluminum sec-butoxide in tetraethylammonium hydroxide (TEAOH) to form an aluminum source, dropwise adding a silicon source into the aluminum source, stirring, oscillating at 80-95 ℃ in an oil bath, aging for 18-24 h, and sequentially adding potassium hydroxide (KOH) solution and hexamethylammonium bromide (C) 12 H 30 Br 2 N 2 ) The solution is fully mixed, and finally, the reaction is carried out for 24 to 120 hours at the temperature of 150 to 175 ℃ to obtain seed crystals; preparing the obtained seed crystal into impregnating solution;
s2: cu is added with 2+ Mixing a source with tetraethylenepentamine to obtain a copper amine complex, sequentially mixing the copper amine complex with cyclohexylamine CHA, pouring the mixture into a mixture of aluminum isopropoxide and phosphoric acid, and stirring at room temperature to prepare gel;
s3: and (3) immersing the cordierite support in an immersion liquid, taking out, then placing in the gel obtained in the step (S2), and finally carrying out hydrothermal preparation in a reaction kettle.
As a preferable aspect of the present inventionIn step S1, the sol molar ratio of the obtained seed crystal is SiO 2 :0.03Al 2 O 3 :(0.08～0.10)KOH:0.82TEAOH:(0.12～0.15)C 12 H 30 Br 2 N 2 :25H 2 O。
In a preferred embodiment of the present invention, in step S1, the seed crystal is a nano-sized particle, and the particle size is 200 to 300nm.
As a preferred embodiment of the present invention, in step S2, the molar ratio of the resulting gel (0.01-0.1) Cu-TEPA:1Al 2 O 3 :1.1P 2 O 5 :0.9CHA:45H 2 O。
In the preferred embodiment of the present invention, in step S2, the copper source and tetraethylenepentamine are mixed, specifically, stirred for 2 hours to form a copper amine complex.
As a preferable mode of the present invention, in the step S2, the molar ratio of the copper amine complex is n (Cu-TEPA)/n (Al) 2 O 3 )＝0.01～0.1。
As a preferable mode of the invention, in the step S3, the concentration of the impregnating solution is 0.5-2 wt%, the times of impregnation are 1-4 times, and the time of each impregnation is 30-90S.
As a preferable scheme of the invention, in the step S3, the preparation method is a one-step hydrothermal synthesis method, the hydrothermal temperature is 190 ℃, and the synthesis time is 12-48 hours.
The invention also discloses a Cu-based SAPO-17 monolithic catalyst, which is prepared by the preparation method according to any one of the above.
The invention also discloses a Cu-based SAPO-17 monolithic catalyst for selectively catalyzing and reducing NO in ammonia x Application to the above.
The beneficial effects of the invention are as follows:
1. the ERI type crystal seed prepared by the invention is crystallized after oil bath oscillation aging to obtain nanoscale crystals (200-300 nm), has elliptic morphology and uniform particle size, has a simple preparation process and is convenient for realizing industrialized mass production.
2. The invention provides a preparation method of an efficient synthetic Cu-based SAPO-17 monolithic catalyst, namely a one-pot method is utilized to rapidly grow a pure-phase continuous SAPO-17 molecular sieve membrane layer on a cheap cordierite support body as a catalyst, compared with a method reported in the related art, the preparation method has the advantages that the preparation process flow is greatly reduced, and meanwhile, the method has simple process, low cost and good repeatability.
3. The synthetic sol for preparing the Cu-based SAPO-17 monolithic catalyst is a mixed gel containing Cu-TEPA, active Cu species are introduced into the sol by adding Cu-TEPA into the sol, and the catalyst is loaded on a cordierite support body to improve the denitration performance of the cordierite support body.
4. The Cu-based SAPO-17 monolithic catalyst has high catalytic performance, and shows excellent catalytic performance, wide catalytic activity window and H resistance in a denitration test 2 O, SO-resistant 2 Performance makes it possible to apply more effectively to coke oven gas, diesel exhaust aftertreatment systems.
Drawings
FIG. 1 shows the XRD pattern of the seed molecular sieve prepared in example 1 of the present invention, (b) is the SEM pattern of the seed;
FIG. 2 is an XRD pattern of Cu-SAPO-17/cordierite monolithic catalysts prepared according to examples 2-4 of the invention, with different concentrations of seed impregnation solutions; (a) standard diffraction peaks of SAPO-17 molecular sieve, (b) characteristic peaks of cordierite support, (c), (d) and (e) are XRD patterns of monolithic catalysis prepared by impregnating solution concentrations of 0.5wt%, 1.0wt% and 2.0wt%, respectively;
FIG. 3 is a graph showing the catalytic activity of the Cu-SAPO-17/cordierite monolithic catalysts prepared in examples 2-4 and comparative example 1 according to the invention, at different seed impregnation levels, (a) 0.5wt%, (b) 1.0wt%, (c) 2.0wt%, and (d) NH for the comparative example Cu-SAPO-17 molecular sieve catalyst 3 -SCR activity map;
FIG. 4 shows examples 5 to 6 of the present invention, in which n (Cu-TEPA)/n (Al 2 O 3 ) SEM image of Cu-SAPO-17/cordierite monolith catalyst synthesized in the following ratio, (a, b) n (Cu-TEPA)/n (Al 2 O 3 )＝0.05，(c，d)n(Cu-TEPA)/n(Al 2 O 3 )＝0.01，(e，f)n(Cu-TEPA)/n(Al 2 O 3 )＝0.1；
FIG. 5 shows the difference n (Cu-TEPA)/n in examples 5 to 6 of the present invention(Al 2 O 3 ) XRD patterns of the Cu-SAPO-17/cordierite monolithic catalyst synthesized in the specific ratio, (a) is a standard diffraction peak of the SAPO-17 molecular sieve, (b) is a characteristic peak of the cordierite support, and (c) and (d) are respectively represented as n (Cu-TEPA)/n (Al) 2 O 3 ) XRD spectrum of monolithic catalyst prepared with =0.01, 0.1;
FIG. 6 shows examples 5 to 6 of the present invention with different n (Cu-TEPA)/n (Al 2 O 3 ) NH of Cu-SAPO-17/cordierite monolithic catalyst synthesized in specific ratio 3 SCR patterns, (a), (b) are respectively expressed as n (Cu-TEPA)/n (Al) 2 O 3 ) Catalytic activity patterns of the monolithic catalysts prepared with the ratios of 0.01 and 0.1;
FIG. 7 shows the production of Cu-SAPO-17/cordierite in the presence of H in (a) according to an embodiment of the invention 2 O and (b) SO-containing 2 NH under simulated flue gas system 3 -SCR activity map;
FIG. 8 is an (a) XRD and (b) SEM images of a Cu-SAPO-17 powder catalyst obtained in comparative example 1.
Detailed Description
The invention starts from the carrier of the catalyst and the preparation method, and is used for researching the Cu-based high-efficiency NH3-SCR catalyst, and the Cu species is replaced into the molecular sieve material by a one-pot method, so that the Cu-SAPO-17/cordierite integral catalyst with high crystallinity and high denitration catalytic performance is obtained, and the technological process for preparing Cu-modified SAPO-17 is greatly reduced.
The first aspect of the object of the present invention: the preparation method of the Cu-based SAPO-17 monolithic catalyst comprises the following steps:
s1, self-preparing seed crystal impregnating solution: dissolving aluminum sec-butoxide in tetraethylammonium hydroxide (TEAOH) to form an aluminum source, dripping a silicon source into the aluminum source, pouring the silicon source into a PP bottle, stirring, carrying out oil bath oscillation aging at 80-95 ℃ for 18-24 h, and sequentially adding KOH solution and C 12 H 30 Br 2 N 2 And (3) fully mixing the solutions, and finally pouring the mixed solution into a stainless steel reaction kettle to react for 24-120 hours at 150-175 ℃ to obtain the seed crystal. The mol ratio of the sol of the obtained seed crystal is SiO 2 :0.03Al 2 O 3 :(0.08～0.10)KOH:0.82TEAOH:(0.12～0.15)C 12 H 30 Br 2 N 2 :25H 2 O. And preparing the obtained silicon-aluminum ERI type molecular sieve into a seed crystal impregnating solution.
S2, preparing synthetic gel: cu is added with 2+ Mixing the source with TEPA to obtain copper amine complex, sequentially mixing with cyclohexylamine, adding into mixture of aluminum isopropoxide and phosphoric acid, stirring at room temperature to obtain gel, and mixing with (0.01-0.1) Cu-TEPA:1Al 2 O 3 :1.1P 2 O 5 :0.9CHA:45H 2 O。
S3, preparing a monolithic catalyst: firstly, preparing the seed crystal obtained in the step S1 into impregnating solution to be loaded on a cordierite support body (impregnation mode is adopted), placing the impregnating solution into the gel obtained in the step S2, and finally preparing the Cu-SAPO-17/cordierite monolithic catalyst in a reaction kettle in a hydrothermal mode.
The invention provides a preparation method of a Cu-based SAPO-17 monolithic catalyst, which adopts a one-pot hydrothermal method to prepare the monolithic catalyst with excellent denitration performance on a low-cost cordierite support body. According to the invention, cu-TEPA is added into a conventional synthesis system, so that Cu species are successfully doped into a molecular sieve framework, and the process flow is simplified; the preparation process adopts a hydrothermal synthesis method to successfully load Cu-SAPO-17 on the cordierite support body, so that the denitration performance of the catalyst is effectively improved. Compared with the traditional molecular sieve catalyst, the monolithic catalyst has more uniform active site distribution, more excellent denitration performance and wider application scene. The invention contemplates the preparation of high performance and pure phase Cu-SAPO-17/cordierite monolithic catalysts on cordierite supports by one-step synthesis in a sol system in the presence of Cu-TEPA. The method can simplify the preparation flow of the integral catalyst, avoid the problems of small Cu species load, uneven distribution and the like, and ensure that the catalyst shows good catalytic performance in a denitration test.
Preferably, in step S1, the seed crystal is nano-sized particles, and the particle size is 200-300 nm. Preferably, the concentration of the impregnating solution in the step S3 is 0.5-2 wt%, the impregnating times are 1-2, and the impregnating time is 30-60S.
Preferably, the Cu in step S2 2+ Source (CuSO) 4 Or Cu (NO) 3 ) 2 ) Mixing TEPA with stirringStirring for 2h to form a copper amine complex.
Preferably, the molar ratio of the copper amine complex in step S2 is n (Cu-TEPA)/n (Al 2 O 3 )＝0.05～0.1。
Preferably, the preparation method in step S3 is a one-pot method.
The second aspect of the object of the invention provides a Cu-based SAPO-17 monolithic catalyst, which is prepared by the preparation method according to any of the above.
The invention aims at providing a third aspect of the Cu-based SAPO-17 monolithic catalyst for denitration.
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the preferred embodiment of the invention, the stirring rotation speed is 350r, the centrifugal rotation speed is 10000r/min, the time is 6min, and the volume of the stainless steel reaction kettle is 100mL.
Example 1
The molar ratio of the oxide of each component of the prepared seed crystal is SiO 2 :0.03Al 2 O 3 :0.10KOH:0.82TEAOH:0.15C 12 H 30 Br 2 N 2 :25H 2 O. The experimental procedure was as follows: adding aluminum sec-butoxide into TEAOH to form an aluminum source, then dropwise adding silica sol to prepare a mixed solution, aging for 20h at 90 ℃ in an oil bath oscillating pot, cooling to room temperature after aging, then sequentially adding KOH solution and hexamethylammonium bromide solution, fully stirring, pouring into a stainless steel reaction kettle, and crystallizing for 120h at 150 ℃ to obtain a final product. And finally, centrifuging the obtained product to be neutral, and drying the product at 80 ℃ for 12 hours to obtain the ERI molecular sieve.
Characterization results: the XRD characterization diagram of the product of this example is shown in FIG. 1, and the obvious diffraction peak of ERI characteristic is shown in (a) of FIG. 1, and no other hetero-crystalline phase exists, which shows that the molecular sieve prepared in this example is a pure phase ERI type molecular sieve. The SEM characterization of the synthesized ERI-type molecular sieve is shown in FIG. 1 (b), from which it can be seen that the molecular sieve obtained is elliptical and has a particle size of about 200-300 nm.
Example 2
Adding tetraethylenepentamine and CuSO into deionized water 4 Fully stirring for 2 hours to form Cu-TEPA, adding cyclohexylamine, stirring for 2 hours to form a mixed solution, and finally pouring the mixed solution into deionized water dissolved with phosphoric acid and aluminum isopropoxide, and fully stirring to form a mixed sol. The proportion (molar ratio) of the oxide forms of the components is 0.05Cu-TEPA:1Al 2 O 3 :1.1P 2 O 5 :0.9CHA:45H 2 O. The seed crystal obtained in example 1 was prepared into an impregnating solution having a mass fraction of 0.5wt%, and cordierite was immersed in the impregnating solution for 90s to carry the seed crystal, and dried in a blast oven at 80℃for 1 hour. And finally, placing the cordierite with the seed crystal and the mixed sol into a stainless steel reaction kettle to react for 24 hours at 190 ℃. The obtained monolithic catalyst was washed with water to neutrality and dried in a forced air oven at 80 ℃ for use.
Characterization results: in FIG. 2, (a) is the diffraction peak of a standard SAPO-17 molecular sieve, (b) is the diffraction peak of a cordierite support, and (c) is the XRD spectrum of the monolithic catalyst prepared in the seed soaking solution, wherein the spectrum has obvious diffraction peaks of the SAPO-17 characteristic and the diffraction peak of the cordierite support, and no other hetero-crystalline phase, so that the prepared product is the pure SAPO-17 monolithic catalyst. The catalyst was subjected to denitration test, the catalytic activity of which is shown in FIG. 3 (a), and it was found that it was NO in the low temperature zone x Poor conversion at temperature>The catalytic activity at 400 ℃ is better.
Example 3
Adding tetraethylenepentamine and CuSO into deionized water 4 Fully stirring for 2 hours to form Cu-TEPA, adding cyclohexylamine, stirring for 2 hours to form a mixed solution, and finally pouring the mixed solution into deionized water dissolved with phosphoric acid and aluminum isopropoxide, and fully stirring to form a mixed sol. The proportion (molar ratio) of the oxide forms of the components is 0.05Cu-TEPA:1Al 2 O 3 :1.1P 2 O 5 :0.9CHA:45H 2 O. The mass fraction of the seed crystal obtained in example 1 was 1.0And (3) immersing the cordierite in the impregnating solution for 60s to load seed crystals, and drying the cordierite in a blast oven at 80 ℃ for 1h. And finally, placing the cordierite loaded with the seed crystal and the mixed sol into a stainless steel reaction kettle for reaction at 190 ℃ for 24 hours. The obtained monolithic catalyst was washed with water to neutrality and dried in a forced air oven at 80 ℃ for use.
Characterization results: the XRD characterization of the monolithic catalyst obtained in FIG. 2 (d) shows distinct diffraction peaks of SAPO-17 and cordierite, and no other hetero-crystalline phase, indicating that the catalyst prepared in this example is a standard SAPO-17 molecular sieve. The monolithic catalyst is subjected to denitration test, the activity diagram is shown as a figure 3 (b), and the monolithic catalyst is found to have 100% NO at 200-500 DEG C x The conversion rate is over 90 percent at 500 ℃, and the denitration performance is excellent. In the SEM characterization of the monolithic catalyst synthesized in this example, it can be found that the surface morphology of the monolithic catalyst obtained by SEM characterization of the monolithic catalyst synthesized in this example is that spheres formed by aggregation of needle-like grains exist on a membrane layer formed by close packing of cubic crystal blocks, and the thickness of the molecular sieve membrane layer is about 20 μm. The self-made seed crystal can be used for successfully inducing the SAPO-17 molecular sieve.
Example 4
Adding tetraethylenepentamine and CuSO into deionized water 4 Fully stirring for 2 hours to form Cu-TEPA, adding cyclohexylamine, stirring for 2 hours to form a mixed solution, and finally pouring the mixed solution into deionized water dissolved with phosphoric acid and aluminum isopropoxide, and fully stirring to form a mixed sol. The proportion (molar ratio) of the oxide forms of the components is 0.05Cu-TEPA:1Al 2 O 3 :1.1P 2 O 5 :0.9CHA:45H 2 O. The impregnation liquid with the mass fraction of 2.0wt% was prepared by immersing cordierite in the impregnation liquid for 30s to carry the seed crystal, and drying the cordierite in a blast oven at 80 ℃ for 1h. And finally, placing the cordierite loaded with the seed crystal and the mixed sol into a stainless steel reaction kettle for reaction at 190 ℃ for 24 hours. The obtained monolithic catalyst was washed with water to neutrality and dried in a forced air oven at 80 ℃ for use.
Characterization results: the (e) in FIG. 2 shows significant diffraction peaks for SAPO-17 and cordierite support, and no other hetero-crystalline phases, indicating that the product is a pure SAPO-17 monolithic catalyst. The activity of the catalyst is shown in figure 3 (c) when the catalyst is subjected to denitration test, the NO conversion rate can reach 100% in the temperature range of 250-400 ℃, but the catalytic activity drops rapidly when the temperature is higher than 400 ℃.
Example 5
Adding tetraethylenepentamine and CuSO into deionized water 4 Fully stirring for 2 hours to form Cu-TEPA, adding cyclohexylamine, stirring for 2 hours to form a mixed solution, and finally pouring the mixed solution into deionized water dissolved with phosphoric acid and aluminum isopropoxide, and fully stirring to form a mixed sol. The proportion (molar ratio) of the oxide forms of the components is 0.01Cu-TEPA:1Al 2 O 3 :1.1P 2 O 5 :0.9CHA:45H 2 O. The seed crystal obtained in example 1 was prepared into an impregnating solution having a mass fraction of 1.0wt%, and cordierite was immersed in the impregnating solution for 90s to carry the seed crystal, and dried in a blast oven at 80℃for 1 hour. And finally, placing the cordierite loaded with the seed crystal and the mixed sol into a stainless steel reaction kettle for reaction at 190 ℃ for 24 hours. The obtained monolithic catalyst was washed with water to neutrality and dried in a forced air oven at 80 ℃ for use.
Characterization results: in FIG. 5, (a) is the diffraction peak of the standard SAPO-17 molecular sieve, (b) is the diffraction peak of the cordierite support, and (c) is n (Cu-TEPA)/n (Al) 2 O 3 ) XRD spectrum of the monolithic catalyst prepared for 0.01 is that the monolithic catalyst only has a diffraction peak of SAPO-17 and a diffraction peak of a cordierite support body, and no other hetero-crystalline phase exists, so that the prepared product is the pure SAPO-17 monolithic catalyst. Fig. 4 (c, d) shows SEM crystal morphology of the surface and cross section of the catalyst, and as can be seen from fig. 4 (c), the crystal is formed by stacking cubic grains having different sizes, and the thickness of the film layer is 30 μm. The activity of the catalyst was measured by denitration, as shown in FIG. 5 (a), and it was found that the catalyst was excellent in denitration activity only in the high temperature range (400 to 600 ℃ C.) because of low temperature Duan Moxing.
Example 6
Adding Tetraethylenepentamine (TEPA) and CuSO to deionized water 4 Fully stirring for 2 hours to form Cu-TEPA, adding cyclohexylamine, stirring for 2 hours to form a mixed solution, finally pouring the mixed solution into deionized water dissolved with phosphoric acid and aluminum isopropoxide, and fully stirring to form a mixed solutionAnd (5) glue. The proportion (molar ratio) of the oxide forms of the components is 0.1Cu-TEPA:1Al 2 O 3 :1.1P 2 O 5 :0.9CHA:45H 2 O. The seed crystal obtained in example 1 was prepared into an impregnating solution having a mass fraction of 1.0wt%, and cordierite was immersed in the impregnating solution for 60s to carry the seed crystal, and dried in a blast oven at 80℃for 1 hour. Finally, placing the cordierite loaded with the seed crystal and the mixed sol into a stainless steel reaction kettle for reaction at 190 ℃ for 48 hours. The obtained monolithic catalyst was washed with water to neutrality and dried in a forced air oven at 80 ℃ for use.
Characterization results: in FIG. 5 (d), only the diffraction peaks characteristic of SAPO-17 and the diffraction peaks of the cordierite support, without other hetero-crystalline phases, indicate that the prepared product is a pure SAPO-17 monolithic catalyst. The surface morphology of the catalyst was observed by SEM in FIG. 4 (e, f) to be a close packing of 50 μm rod-like grains, and the film thickness was 25. Mu.m. The catalyst was subjected to a denitration test, the activity of which is shown in fig. 6 (b), and the catalytic activity window was found to be in a narrower middle-high temperature section (250-400 c) compared with example 2, probably due to the fact that the high-temperature catalytic activity of the catalyst was inhibited by too high content of Cu species in the catalyst.
Example 7
Adding tetraethylenepentamine and Cu (NO) into deionized water 3 ) 2 Fully stirring for 2 hours to form Cu-TEPA, adding cyclohexylamine, stirring for 2 hours to form a mixed solution, and finally pouring the mixed solution into deionized water dissolved with phosphoric acid and aluminum isopropoxide, and fully stirring to form a mixed sol. The proportion (molar ratio) of the oxide forms of the components is 0.05Cu-TEPA:1Al 2 O 3 :1.1P 2 O 5 :0.9CHA:45H 2 O. The seed crystal obtained in example 1 was prepared into an impregnating solution having a mass fraction of 1.0wt%, and cordierite was immersed in the impregnating solution for 90s to carry the seed crystal, and dried in a blast oven at 80℃for 1 hour. And finally, placing the cordierite loaded with the seed crystal and the mixed sol into a stainless steel reaction kettle for reaction at 190 ℃ for 24 hours. The obtained monolithic catalyst was washed with water to neutrality and dried in a forced air oven at 80 ℃ for use.
Characterization results: to test catalyst pair H 2 O and SO 2 Tolerance to H was performed on it 2 O and SO 2 Stability against stressAnd (5) testing. FIGS. 7 and 8 show the resulting Cu-SAPO-17/cordierite monolith catalyst in the presence of H 2 O and SO 2 NH under simulated flue gas system 3 -SCR performance map. As can be seen from the figure, the addition of the whole process water has no effect on the activity of the catalyst, while the SO is introduced 2 3.5 After h, NO of the catalyst x The conversion began to drop, only to 94% at 7 hours; at this time remove SO 2 After 1h, its activity was restored. This indicates that the Cu-SAPO-17/cordierite monolithic catalyst has excellent water and sulfur resistance stability.
Comparative example 1
Adding tetraethylenepentamine and CuSO into deionized water 4 Fully stirring for 2 hours to form Cu-TEPA, adding cyclohexylamine, stirring for 2 hours to form a mixed solution, and finally pouring the mixed solution into deionized water dissolved with phosphoric acid and aluminum isopropoxide, and fully stirring to form a mixed sol. The proportion (molar ratio) of the oxide forms of the components is 0.05Cu-TEPA:1Al 2 O 3 :1.1P 2 O 5 :0.9CHA:45H 2 O. 0.5wt% of the seed crystal obtained in example 1 was added to the sol, and the mixture was crystallized at 190℃for 24 hours. And finally, boiling, centrifuging, drying and grinding the obtained product for later use.
Characterization results: FIG. 8 is an XRD and SEM plot of a synthesized powdered Cu-SAPO-17 catalyst, wherein the product is a SAPO-17 molecular sieve, as can be seen by comparison with standard characteristic peaks, and no diffraction peak of Cu species is found in the XRD plot, probably due to relatively uniform distribution of Cu species in crystals, and a denitration test is performed on the sample, so that the highest conversion of the catalyst at 350 ℃ is 55%, as shown in FIG. 3 (d). Much lower NH than monolithic catalysts 3 -SCR catalytic performance.
The catalytic performance test conditions for the monolithic catalysts of examples 2-7 described above were: 500ppm NO, 500ppm NH 3 5% by volume of O 2 ，N 2 As a reaction equilibrium gas. The total flow rate of the reaction gas was fixed at 100mL min -1 Space Velocity (WHSV) of 60,000h -1 . Whereas comparative example 1: pressing the powder catalyst into particles, sieving, selecting the catalyst with particle size of 40-60 meshes, and weighingA sample of 0.1g of the catalyst was placed in a U-shaped reaction tube and then tested under the test conditions described above.
The foregoing examples have shown only the preferred embodiments of the invention, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be pointed out that various other corresponding changes and modifications can be made by those skilled in the art in light of the above description of the technical solution and the idea, and all such changes and modifications are intended to be within the scope of the invention as defined in the appended claims.
Claims (10)
1. The preparation method of the Cu-based SAPO-17 monolithic catalyst is characterized by comprising the following steps of:
s1: dissolving aluminum sec-butoxide in tetraethylammonium hydroxide (TEAOH) to form an aluminum source, dropwise adding a silicon source into the aluminum source, stirring, oscillating at 80-95 ℃ in an oil bath, aging for 18-24 h, and sequentially adding potassium hydroxide (KOH) solution and hexamethylammonium bromide (C) 12 H 30 Br 2 N 2 ) Fully mixing the solution, finally carrying out reaction at 150-175 ℃ for 24-120 h to obtain seed crystals, and preparing the obtained seed crystals into impregnating solution;
s2: cu is added with 2+ Mixing a source with Tetraethylenepentamine (TEPA) to obtain a Cu-TEPA copper amine complex, sequentially mixing with Cyclohexylamine (CHA), pouring into a mixture of aluminum isopropoxide and phosphoric acid, and stirring at room temperature to prepare gel;
s3: and (3) immersing the cordierite support in an immersion liquid, taking out, then placing in the gel obtained in the step (S2), and finally carrying out hydrothermal preparation in a reaction kettle.
2. The method for preparing a Cu-based SAPO-17 monolithic catalyst as defined in claim 1, wherein in step S1, the sol molar ratio of the obtained seed crystal is SiO 2 :0.03Al 2 O 3 :(0.08～0.10)KOH:0.82TEAOH:(0.12～0.15)C 12 H 30 Br 2 N 2 :25H 2 O。
3. The method for preparing a Cu-based SAPO-17 monolithic catalyst as claimed in claim 1, wherein in step S1, the seed crystal is nano-sized particles with a particle size of 200 to 300nm.
4. The method for preparing a Cu-based SAPO-17 monolithic catalyst as defined in claim 1, wherein in step S2, the molar ratio of the obtained gel (0.01-0.1) Cu-TEPA:1Al 2 O 3 :1.1P 2 O 5 :0.9CHA:45H 2 O。
5. The method for preparing a Cu-based SAPO-17 monolithic catalyst as recited in claim 1, wherein in step S2, the Cu 2+ The source and tetraethylenepentamine are mixed, in particular, stirred for 2 hours to form a copper amine complex.
6. The method for preparing a Cu-based SAPO-17 monolithic catalyst as claimed in claim 1, wherein in step S2, the molar ratio of the copper amine complex is n (Cu-TEPA)/n (Al) 2 O 3 )＝0.01～0.1。
7. The method for preparing a Cu-based SAPO-17 monolithic catalyst as claimed in claim 1, wherein in step S3, the concentration of the impregnating solution is 0.5 to 2wt%, the number of times of impregnation is 1 to 4, and the time of each impregnation is 30 to 90S.
8. The method for preparing a Cu-based SAPO-17 monolithic catalyst as claimed in claim 1, wherein in step S3, the preparation method is a one-step hydrothermal synthesis method, the hydrothermal temperature is 190 ℃, and the synthesis time is 12-48 hours.
Cu-based SAPO-17 monolithic catalyst, characterized in, that it is obtainable by the preparation method according to any one of claims 1 to 8.
10. A Cu-based SAPO-17 monolithic catalyst as claimed in claim 9 for ammonia selective catalytic reduction of NO x Application to the above.
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