CN113000063A - Fe, Cu-SSZ-13 molecular sieve with Cu and Fe occupying different sites and preparation method thereof - Google Patents
Fe, Cu-SSZ-13 molecular sieve with Cu and Fe occupying different sites and preparation method thereof Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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Abstract
The invention relates to a Fe, Cu-SSZ-13 molecular sieve with Cu and Fe occupying different sites, wherein Cu simultaneously occupies the positions of a six-membered ring and an eight-membered ring in a CHA structure and is taken as NOxAnd Fe occupies the position of the eight-membered ring in the CHA structure as NOxTo catalyze the catalytic sites at high temperatures. The invention has the beneficial effects that: the invention utilizes the characteristic that the low-temperature activity of Cu-SSZ-13 is only from Cu on a six-membered ring, obtains the Fe, Cu-SSZ-13 molecular sieve with high and low-temperature activity by exchanging Cu on an eight-membered ring with Fe, and effectively overcomes the defect that the Fe-SSZ-13 molecular sieve with high Fe load capacity is difficult to prepare due to large hydration radius of Fe ionsDifficulty, and the synergistic action between the Cu catalytic site and the Fe catalytic site.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a double-site Fe, Cu-SSZ-13 molecular sieve catalyst and a preparation method thereof.
Background
SSZ-13 is a Chabazite (CHA) structured aluminosilicate molecular sieve, first successfully synthesized by Zones of Chevron oil company, USA in 1985 (US 4544538), with a pore size of 0.38nm x 0.38nm and a specific surface area of 700m2(ii) in terms of/g. Due to its unique pore structure, large specific surface area, good hydrothermal stability and shape-selective function, the SSZ-13 molecular sieve has received much attention in academia and industry. With further development of the technology, researchers load transition metals into the SSZ-13 molecular sieve to obtain corresponding catalytic properties. The Cu-SSZ-13 molecular sieve loads Cu ions into the SSZ-13 molecular sieve, and Nitrogen Oxide (NO)x) Excellent catalytic activity in selective catalytic reduction reaction, N2Selectivity and hydrothermal stability. The research finds that two types of catalytic sites exist in the Cu-SSZ-13 molecular sieve, and at low Cu loading, Cu is added2+Ions exist in the six-membered ring unit of the CHA structure and are stable, and Cu is added along with the increase of the loading amount2+Ions gradually occupy eight-membered ring units in the CHA structure (j.cat., 2013,300, 20.; chem.commun.,2012,48, 4758). For NOxSelective catalytic reduction of Cu on the six-membered ring in Cu-SSZ-13 molecular sieves2+Mainly contributing to the catalytic activity at low temperatures, and Cu on the eight-membered ring2+Mainly contributing to the catalytic activity at high temperatures. Like the Cu-SSZ-13 molecular sieve, the Fe-SSZ-13 molecular sieve loads Fe ions into the structure of the SSZ-13 molecular sieve. Fe-SSZ-13 molecular sieves for NO, in contrast to Cu-SSZ-13 molecular sievesxSelective catalytic activity at low temperature: (<At 300 ℃) is higher thanPoor, however, at high temperatures: (>500 c) showed better activity and received much attention.
At present, the Cu-SSZ-13 molecular sieve enters a large-scale production stage at home and abroad, but the large-scale preparation of the Fe-SSZ-13 molecular sieve is rarely reported, mainly because the synthesis of the Fe-SSZ-13 molecular sieve is difficult, and the essential reason is that Fe3+Or Fe2+Has a large hydration radius and is difficult to enter into the structure of SSZ-13. In view of Fe2+Has a smaller hydration radius than Fe3+So FeSO is generally adopted in literature reports4·7H2Preparation of Fe-SSZ-13 molecular sieve by using O as iron source for exchange, in order to prevent Fe2+Oxidation and Fe (OH)2Or Fe (OH)3The exchange reaction needs to be carried out under the protection of high-purity nitrogen and weak acidity, and the subsequent drying process also needs to be carried out under the protection of high-purity nitrogen (ACS Catal.2016,6,2939). It is noteworthy that the high Fe-loaded Fe-SSZ-13 molecular sieves, which are difficult to prepare even under such severe conditions, are very likely to contain Fe in the product2O3Impurities, which may be present in the Fe-SSZ-13 channels, may also be a heterogeneous phase. Although there is a patent (CN 105214720B), a Cu/Fe-SSZ-13 molecular sieve is prepared by injecting a metal salt precursor of Cu/Fe into an SSZ-13 molecular sieve pore channel by an impregnation method under air and then by a high-temperature calcination method. However, from the experimental process and data reported in the patent, in combination with the current literature reports, it is believed that the products prepared therefrom are likely to be miscible, mainly SSZ-13, Cu-SSZ-13, CuO and Fe2O3A mixture of nanoparticles. Even if Fe-SSZ-13 is present in the product, it is likely to be very small because simple physical impregnation does not allow hydrated Fe ions to enter the structure of SSZ-13.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a Fe, Cu-SSZ-13 molecular sieve with Cu and Fe occupying different sites and a preparation method thereof.
The Cu and the Fe occupy different sites of the Fe, Cu-SSZ-13 molecular sieve, and the Cu simultaneously occupies the positions of a six-membered ring and an eight-membered ring in the CHA structureIn the CHA structure (Cu predominantly occupies a stable six-membered ring position) as NOxThe selective catalytic reaction of (1) takes place at a low temperature (100-350 ℃), Fe occupies the position of an eight-membered ring in the CHA structure and is taken as NOxThe catalytic sites of the selective catalytic reaction at high temperature (350-600 ℃).
The application of the Fe, Cu-SSZ-13 molecular sieve with Cu and Fe occupying different sites can be applied to selective catalytic reduction of nitrogen oxides at a wide temperature range, namely 100-600 ℃, the contribution of low-temperature activity mainly comes from Cu and the synergistic effect of Cu and Fe, and the contribution of high-temperature activity mainly comes from Fe.
The preparation method of the Fe, Cu-SSZ-13 molecular sieve with Cu and Fe occupying different sites comprises the following steps:
s1, mixing Na-SSZ-13 molecular sieve with excessive NH4 +NH is prepared by exchanging for 12h under heating condition (80℃)4-a SSZ-13 molecular sieve;
s2, reacting with NH under heating conditions by using excessive Cu source4-SSZ-13 molecular sieve exchange to produce Cu-SSZ-13 with high Cu content;
s3, finally exchanging Cu on the eight-membered ring in the Cu-SSZ-13 structure by ferrous ions at low temperature under stirring to obtain the Fe, Cu-SSZ-13 molecular sieve (Cu ions stable on the six-membered ring are difficult to exchange at low temperature, and Cu ions on the eight-membered ring are easy to exchange, considering hydrated Fe2+So that Cu ions can only be exchanged on the eight-membered ring at low temperature), comprising the steps of: adding 1g of Cu-SSZ-13 molecular sieve into an aqueous solution (50mL) containing ferrous ions with a certain concentration, stirring at a low temperature for a certain time, centrifuging or filtering and drying, and calcining the obtained product at 550 ℃ for 2h to obtain the Fe, Cu-SSZ-13 molecular sieve.
Preferably, the method comprises the following steps: in the step S1, NH4 +Includes NH4NO3、CH3COONH4Or (NH)4)2SO4； NH4 +The molar ratio of the molecular sieve to Al in the SSZ-13 molecular sieve is more than 5; the Si/Al atomic ratio of the adopted SSZ-13 molecular sieve is 6-20, preferably 9-12.
Preferably, the method comprises the following steps: in the step S2, the Cu source includes CuSO4And hydrates thereof, CuCl2And hydrates thereof or Cu (CH)3COO)2And hydrates thereof, preferably CuSO4And hydrates thereof; cu source and NH4-the molar ratio of Al in the SSZ-13 molecular sieve is greater than 5; the Cu/Al molar ratio in the prepared Cu-SSZ-13 with high Cu content is more than 0.25.
Preferably, the method comprises the following steps: in the step S3, the stirring temperature at low temperature is 10-50 ℃, preferably 20-30 ℃; the stirring time is 6-24 h, preferably 16 h.
Preferably, the method comprises the following steps: in the step S3, the ferrous ions include FeSO4And hydrates thereof, FeCl2And hydrates thereof or Fe (CH)3COO)2And hydrates thereof, preferably FeSO4And hydrates thereof.
Preferably, the method comprises the following steps: in the step S3, the concentration of the ferrous ion aqueous solution is 0.02-0.2 mol/L.
Preferably, the method comprises the following steps: in the step S3, the molar ratio of Fe to Cu of the Fe, Cu-SSZ-13 molecular sieve is 0.05-0.30.
Preferably, the method comprises the following steps: in the step S3, the molar ratio of (Cu + Fe)/Al of the Fe, Cu-SSZ-13 molecular sieve is 0.2-0.3.
The invention has the beneficial effects that: the invention utilizes the characteristic that the low-temperature activity of Cu-SSZ-13 is only from Cu on a six-membered ring, obtains the Fe, Cu-SSZ-13 molecular sieve with high and low-temperature activity by exchanging Cu on an eight-membered ring with Fe, effectively overcomes the difficulty that the Fe-SSZ-13 molecular sieve with high Fe load is difficult to prepare due to large hydration radius of Fe ions, and simultaneously has synergistic action between Cu catalytic sites and Fe catalytic sites.
Drawings
FIG. 1 is an XRD pattern of a Cu-SSZ-13 molecular sieve, Fe, Cu-SSZ-13 molecular sieve, produced in examples 1-4 of the present invention;
FIG. 2 is a TEM-mapping chart of Fe, Cu-SSZ-13 molecular sieve prepared in example 3 of the present invention;
wherein a) to f) in fig. 2 are: a) dark field TEM image; b) TEM-mapping graph of Si element; c) an Al element TEM-mapping graph; d) a Cu element TEM-mapping image; e) a TEM-mapping picture of Fe element; f) si + Al + Cu + Fe element TEM-mapping picture;
FIG. 3 is a graph of the temperature-NO conversion for Fe, Cu-SSZ-13 molecular sieves made in examples 2-4 of the present invention;
FIG. 4 is a graph of the temperature-NO conversion for the Fe, Cu-SSZ-13 molecular sieve made in example 3 of this invention.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are set forth merely to aid in the understanding of the invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Unlike the traditional method of preparing Fe-SSZ-13 molecular sieve under heating condition, the invention adopts the method of preparing Fe-SSZ-13 molecular sieve at low temperature<Partially exchanging Cu sites in the Cu-SSZ-13 molecular sieve with high Cu load at 30 ℃ to prepare the Fe, Cu-SSZ-13 molecular sieve. In the case of the high Cu loading Cu-SSZ-13 molecular sieve, Cu occupies the sites of a six-membered ring and an eight-membered ring in the SSZ-13 structure at the same time. In Cu-SSZ-13 molecular sieve and Fe2+Due to Fe during the exchange process2+The radius of the hydrated ion is large, and the Cu ion which is stable on a six-membered ring in the Cu-SSZ-13 molecular sieve at low temperature is difficult to be Fe2+Exchange, the exchange process occurs mainly on the eight-membered ring in its structure. Because stable Cu ions on a six-membered ring in the Cu-SSZ-13 molecular sieve are catalytic sites of low-temperature SCR, the prepared Fe, Cu-SSZ-13 molecular sieve not only maintains the excellent low-temperature SCR catalytic activity of the Cu-SSZ-13 molecular sieve, but also has high-temperature catalytic activity due to the introduction of the Fe sites.
Example 1
Preparation of Cu-SSZ-13 molecular sieve:
weighing 10g of SSZ-13 molecular sieve with the silicon-aluminum ratio of 12, adding the molecular sieve into 50mL of ammonium nitrate solution with the concentration of 0.1mol/L, reacting for 3h under an oil bath at 80 ℃, centrifuging and washing after the reaction is finished, transferring the product into a blast drying oven, and drying at 120 ℃ to obtain NH4SSZ-13 powder. Weighing 3g of NH4SSZ-13 molecular sieves added to 10mL of CuSO at a concentration of 0.5mol/L4Reacting the solution at 80 ℃ for 3h, centrifuging, washing and drying in a forced air drying oven. And grinding the dried product, and then transferring the product to a muffle furnace to roast for 4 hours at 550 ℃ to obtain the Cu-SSZ-13 molecular sieve.
Example 2
Preparation of Fe, Cu-SSZ-13 molecular sieve:
50mL of FeSO with the concentration of 0.05mol/L is measured4The solution was put into a 100mL beaker, 1g of the Cu-SSZ-13 molecular sieve prepared in example 1 was added into the beaker, and after stirring for 16 hours at 25 ℃, the mixture was centrifuged, washed and transferred to a forced air drying oven to be dried at 80 ℃ to obtain Fe, Cu-SSZ-13 molecular sieve coarse powder, and after being sufficiently ground, the coarse powder was transferred to a muffle furnace to be calcined at 550 ℃ for 4 hours to obtain Fe, Cu-SSZ-13 molecular sieve with the sample number of Fe, Cu-SSZ-13 (# 1).
Example 3
Preparation of Fe, Cu-SSZ-13 molecular sieve:
FeSO obtained in example 24The concentration of the solution is changed to 0.1mol/L, and other preparation steps are consistent. The sample number is Fe, Cu-SSZ-13(2 #).
Example 4
Preparation of Fe, Cu-SSZ-13 molecular sieve:
FeSO obtained in example 24The concentration of the solution is changed to 0.2mol/L, and other preparation steps are consistent. The sample number is Fe, Cu-SSZ-13(3 #).
Example 5
The elemental analysis results of examples 2-4 are shown in Table 1, along with FeSO4The concentration of the solution is increased, the content of Fe in the prepared Fe, Cu-SSZ-13 molecular sieve is gradually increased, and the content of Cu is gradually reduced. However, the exchange amount of Fe is low as a whole even if FeSO of high concentration is used4Solution exchange also makes it difficult to significantly increase the amount of Fe exchanged, and as a result, Fe can only partially exchange Cu on the more readily exchanged eight-membered ring of the Cu-SSZ-13 molecular sieve, consistent with expectations. XRD of samples of examples 2-4 As shown in FIG. 1, XRD diffraction peaks of Fe, Cu-SSZ-13 molecular sieve are slightly shifted to the left overall in comparison with that of Cu-SSZ-13 molecular sieve, indicating that the introduction of Fe makes the diffraction peak position slightly shifted to the left overallThe unit cell parameters of the Cu-SSZ-13 molecular sieve are slightly increased. Nevertheless, the shape and position of the diffraction peak of the Fe, Cu-SSZ-13 molecular sieve substantially coincided with those of the Cu-SSZ-13 molecular sieve, and no other diffraction peak was observed. The TEM-mapping of the Fe, Cu-SSZ-13(2#) molecular sieve is shown in FIG. 2. In a single Fe, Cu-SSZ-13 crystal particle, Cu and Fe elements are uniformly distributed, and the condition that the Fe element is locally enriched in the crystal particle is not found, which indicates that the Fe element does not exist in the form of Fe oxide nano particles, but is in the framework of the SSZ-13 molecular sieve crystal structure. The ICP elemental analysis results of the Fe, Cu-SSZ-13 molecular sieves prepared in examples 2-4 of the present invention are shown in Table 1 below.
TABLE 1 ICP elemental analysis results for Fe, Cu-SSZ-13 molecular sieves prepared in inventive examples 2-4
| Sample numbering | Si(mg/kg) | Al(mg/kg) | Cu(mg/kg) | Fe(mg/kg) | Fe/Al(mol) |
| Fe,Cu-SSZ-13(1#) | 360734 | 35938 | 23597 | 1316 | 0.018 |
| Fe,Cu-SSZ-13(2#) | 370335 | 36015 | 20631 | 2418 | 0.032 |
| Fe,Cu-SSZ-13(3#) | 367912 | 35129 | 19826 | 3085 | 0.042 |
Nitrogen oxide selective catalytic reduction test conditions: [ NO ]]＝[NH3]＝500ppm；[O2]＝10％，[H2O]＝10％， N2Balancing; airspeed 70000h-1. (wherein [ O ]2]＝10％，[H2O]10% represents volume percentage)
The test results are shown in fig. 3, the catalytic performance of the Fe, Cu-SSZ-13 molecular sieve is improved with the increase of the Fe loading, which is mainly due to the contribution of the Fe sites to the high temperature catalytic activity and the synergistic catalytic effect between the Cu catalytic sites and the Fe catalytic sites. It is noted that the Fe, Cu-SSZ-13 molecular sieve has a very small Fe content, even though the Fe, Cu-SSZ-13(3#) molecular sieve has a Fe/Al molar ratio of only 0.042. This shows that trace amount of Fe can obviously improve the catalytic performance of the Fe, Cu-SSZ-13 molecular sieve. At 100-350 ℃, the catalytic performances of Fe, Cu-SSZ-13(2#) and Fe, Cu-SSZ-13(3#) are basically consistent, and at 350-500 ℃, the catalytic performances of Fe, Cu-SSZ-13(2#) are lower than that of Fe, Cu-SSZ-13(3#), whereas at 500-550 ℃, the catalytic performances of Fe, Cu-SSZ-13(2#) are obviously higher than that of Fe, Cu-SSZ-13(3 #). This shows that although Fe, Cu-SSZ-13(3#) has higher performance than Fe, Cu-SSZ-13(2#) in the range of 350-500 ℃ due to the higher content of Fe, some Fe oxide clusters or nanoparticles may exist in Fe, Cu-SSZ-13(3#), and the catalytic performance is rapidly reduced with the continuous increase of temperature.
Claims (10)
1. An Fe, Cu-SSZ-13 molecular sieve with Cu and Fe occupying different sites, which is characterized in that: cu occupies both six-and eight-membered ring positions in the CHA structure as NOxThe selective catalytic reaction of (A) is carried out on catalytic sites at the temperature of 100-350 ℃; fe occupies the position of the eight-membered ring in the CHA structure as NOxThe selective catalytic reaction of the catalytic sites is carried out at the temperature of 350-600 ℃.
2. Use of a Cu, Cu-SSZ-13 molecular sieve according to claim 1, wherein the Cu, Fe occupy different sites, characterized in that: the method is applied to selective catalytic reduction of nitrogen oxides in a wide temperature range, wherein the wide temperature range is 100-600 ℃.
3. A method for preparing the Fe, Cu-SSZ-13 molecular sieve occupying distinct sites by Cu, Fe according to claim 1, comprising the steps of:
s1, mixing Na-SSZ-13 molecular sieve with excessive NH4 +Preparation of NH by exchange under heating4-a SSZ-13 molecular sieve;
s2, reacting with NH under heating conditions by using excessive Cu source4-SSZ-13 molecular sieve exchange to produce Cu-SSZ-13 with high Cu content;
s3, finally exchanging Cu on an eight-membered ring in the Cu-SSZ-13 structure by ferrous ions under the stirring condition to obtain the Fe, Cu-SSZ-13 molecular sieve, wherein the steps comprise: adding the Cu-SSZ-13 molecular sieve into an aqueous solution containing ferrous ions with a certain concentration, stirring for a certain time at a low temperature, centrifuging or filtering and drying, and calcining the obtained product to obtain the Fe, Cu-SSZ-13 molecular sieve.
4. The method of claim 3, wherein the Cu, Cu-SSZ-13 molecular sieve comprises Cu and Fe occupying different sites, and the method comprises the following steps: in the step S1, NH4 +Includes NH4NO3、CH3COONH4Or (NH)4)2SO4；NH4 +The molar ratio of the molecular sieve to Al in the SSZ-13 molecular sieve is more than 5; the Si/Al atomic ratio of the adopted SSZ-13 molecular sieve is 6-20.
5. The method of claim 3, wherein the Cu, Cu-SSZ-13 molecular sieve comprises Cu and Fe occupying different sites, and the method comprises the following steps: in the step S2, the Cu source includes CuSO4And hydrates thereof, CuCl2And hydrates thereof or Cu (CH)3COO)2And hydrates thereof; cu source and NH4-the molar ratio of Al in the SSZ-13 molecular sieve is greater than 5; the Cu/Al molar ratio in the prepared Cu-SSZ-13 with high Cu content is more than 0.25.
6. The method of claim 3, wherein the Cu, Cu-SSZ-13 molecular sieve comprises Cu and Fe occupying different sites, and the method comprises the following steps: in the step S3, the stirring temperature range at low temperature is 10-50 ℃, and the stirring time is 6-24 h.
7. The method of claim 3, wherein the Cu, Cu-SSZ-13 molecular sieve comprises Cu and Fe occupying different sites, and the method comprises the following steps: in the step S3, the ferrous ions include FeSO4And hydrates thereof, FeCl2And hydrates thereof or Fe (CH)3COO)2And hydrates thereof.
8. The method of claim 3, wherein the Cu, Cu-SSZ-13 molecular sieve comprises Cu and Fe occupying different sites, and the method comprises the following steps: in the step S3, the concentration of the ferrous ion aqueous solution is 0.02-0.2 mol/L.
9. The method of claim 3, wherein the Cu, Cu-SSZ-13 molecular sieve comprises Cu and Fe occupying different sites, and the method comprises the following steps: in the step S3, the molar ratio of Fe to Cu of the Fe, Cu-SSZ-13 molecular sieve is 0.05-0.30.
10. The method of claim 3, wherein the Cu, Cu-SSZ-13 molecular sieve comprises Cu and Fe occupying different sites, and the method comprises the following steps: in the step S3, the molar ratio of (Cu + Fe)/Al of the Fe, Cu-SSZ-13 molecular sieve is 0.2-0.3.
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|---|---|---|---|---|
| CN113213505A (en) * | 2021-06-23 | 2021-08-06 | 吉林大学 | SSZ-13 molecular sieve, preparation method thereof and Cu-SSZ-13 molecular sieve |
| CN113275035A (en) * | 2021-07-23 | 2021-08-20 | 山东国瓷功能材料股份有限公司 | Bulk phase Fe-doped Cu-SSZ-13 molecular sieve and preparation method and application thereof |
| CN115779959A (en) * | 2022-12-29 | 2023-03-14 | 沈阳师范大学 | Method for preparing CuFe-SSZ-13 molecular sieve catalyst through low-temperature ion exchange and application thereof |
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