CN114477221A - ZK-5 molecular sieve and preparation method and application thereof - Google Patents
ZK-5 molecular sieve and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of molecular sieves, in particular to a ZK-5 molecular sieve and a preparation method and application thereof. The preparation method of the molecular sieve adopts ZK-5 seed crystals to replace an organic template agent, avoids high pollution caused by the organic template agent in the synthesis process, reduces the influence on the environment and simultaneously reduces the synthesis cost of the catalyst; h is also added into the synthetic raw materials2O2The synthesis time of the molecular sieve is effectively shortened, the energy consumption in the preparation process of the molecular sieve is greatly reduced, the synthesis cost of the molecular sieve is reduced, meanwhile, the prepared ZK-5 molecular sieve has high crystallinity and contains a large number of active sites, and the Cu-ZK-5 molecular sieve catalyst prepared by the molecular sieve also has high catalytic activity.
Description
Technical Field
The invention belongs to the technical field of molecular sieves, and particularly relates to a ZK-5 molecular sieve and a preparation method and application thereof.
Background
The emission of a large amount of nitrogen oxides (NOx) can cause environmental pollution problems such as greenhouse effect, acid rain, ozone layer damage and the like, the human health is seriously harmed, and the emission control standard of NOx in countries all over the world is gradually tightenedAnd (4) grid. Ammonia selective catalytic reduction process (NH)3SCR) is known as the most efficient and mature process for removing nitrogen oxides, and the method utilizes ammonia, urea and the like as reducing agents to selectively reduce NO in flue gas into N under the action of catalysts2And H2And O. Transition metal (Cu, Co, etc.) exchanged ZSM-5 molecular sieve catalysts are reported to have higher NH3After SCR performance, copper-based FAU, MOR, BETA, etc. were successively investigated for NOx removal by SCR technology, and all had good denitration performance.
The KFI topological structure molecular sieve consists of Pau cages, Ita cages and D6Rs, and the eight-membered ring pore diameter is
According to research, the excellent topological structure of the molecular sieve can also enable the molecular sieve to show excellent NH3-SCR catalytic performance. However, in the prior art, the molecular sieve needs to be prepared by using an organic template, the use of a large amount of organic template can cause a large amount of industrial toxic waste gas generated in the calcination process of the catalyst, which is not beneficial to environmental management, and in addition, the longer synthesis time also causes the problems of higher energy consumption and higher synthesis cost.
Disclosure of Invention
Aiming at the technical problems of pollution in the preparation process of the ZK-5 molecular sieve, high energy consumption caused by long synthesis time and high synthesis cost in the prior art, the invention provides the preparation method of the ZK-5 molecular sieve, which avoids the use of an organic template in the preparation process, has short synthesis time, and has the characteristics of environmental friendliness, no pollution and low energy consumption.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
in a first aspect, the embodiment of the invention provides a preparation method of a ZK-5 molecular sieve, which comprises the following steps: the method specifically comprises the following steps:
s1: dissolving a soluble aluminum source and an alkali metal compound in water to obtain a clear solution;
s2: mixing a silicon source, strontium nitrate, ZK-5 seed crystal, water and hydrogen peroxide, and stirring to prepare gel;
s3: and (3) dropwise adding the clear solution obtained in the step (S1) into the gel obtained in the step (S2), uniformly mixing, standing for crystallization, and washing, drying and calcining the obtained product to obtain the ZK-5 molecular sieve.
Compared with the prior art, the ZK-5 molecular sieve is prepared by adopting a method without an organic template, and the ZK-5 seed crystal is adopted to replace the organic template, so that high pollution caused by the organic template in the synthesis process is avoided, the influence on the environment is reduced, and the synthesis cost of the catalyst is also reduced; h is also added into the synthetic raw materials2O2The synthesis time of the molecular sieve is effectively shortened, the energy consumption in the preparation process of the molecular sieve is greatly reduced, the synthesis cost of the molecular sieve is reduced, meanwhile, the prepared ZK-5 molecular sieve has high crystallinity and contains a large number of active sites, and the molecular sieve catalyst prepared by the molecular sieve also has high catalytic activity.
Preferably, the aluminum source in S1 is a soluble salt or alkali containing aluminum, and specifically, at least one of aluminum hydroxide, aluminum isopropoxide, aluminum nitrate or sodium metaaluminate can be used; the alkali metal compound is soluble salt or alkali containing potassium element, and specifically potassium hydroxide or potassium chloride can be used.
Preferably, the aluminum element in the aluminum source in S1 is Al2O3The potassium element in the solid alkali metal compound is counted as K2Calculated as O, Al2O3And K2The mass ratio of O is 1: 2 to 2.5.
Preferably, the silicon source in S2 is at least one of water glass, silica sol, sodium silicate, fumed silica and silica white.
Preferably, the silicon element in the silicon source in S2 is SiO2Calculated by SrO, and the aluminum element in the aluminum source in S1 is Al2O3The ratio of the aluminum source in S1 to the silicon source, strontium nitrate and hydrogen peroxide in S2 is calculated as Al2O3：SiO2：SrO：H2O21: 9-11: 0.08-0.12: 0.2 to 0.6; the mass ratio of the aluminum source in S1 to the ZK-5 seed crystal in S2 is 100: 5 to 30, the ratio of the total amount of water used in S1 and S2 to the amount of aluminum source in S1 is 150 to 170: 1.
the optimized raw material dosage can improve the utilization rate of the raw materials and the crystallinity of the ZK-5 molecular sieve product, improve the quality of the ZK-5 molecular sieve product and ensure the application performance of the ZK-5 molecular sieve product. The optimized dosage of the seed crystal can ensure the crystallinity and the finished product quality of the ZK-5 molecular sieve, improve the service performance of the molecular sieve, avoid the mutual attraction of nano particles in the preparation process to cause the partial growth of aggregate particles, reduce the specific surface area of crystal grains, influence the number of active sites in the molecular sieve and reduce the activity of a catalyst.
Preferably, the crystallization temperature in the crystallization process of S3 is 130-180 ℃, the crystallization time is 2.5-3.5 d, more preferably 130-160 ℃, and the crystallization time is 3-3.5 d.
In a second aspect, the embodiment of the invention also provides the ZK-5 molecular sieve prepared by the preparation method.
In a third aspect, the embodiment of the invention also provides the application of the ZK-5 molecular sieve in preparing a Cu-ZK-5 molecular sieve catalyst.
In a fourth aspect, the embodiment of the present invention further provides a method for preparing a Cu-ZK-5 molecular sieve catalyst by using the ZK-5 molecular sieve, which specifically includes the following steps:
step 1: mixing the ZK-5 molecular sieve with an ammonium salt solution, performing ion exchange, washing and drying, and repeating for 2-3 times to obtain an H-ZK-5 molecular sieve;
step 2: and (2) mixing the H-ZK-5 molecular sieve obtained in the step (1) with a copper salt solution, performing ion exchange, washing, drying, and roasting to obtain the Cu-ZK-5 molecular sieve catalyst.
Preferably, the ammonium salt solution in the step 1 is at least one of ammonium chloride, ammonium acetate, ammonium sulfate or an ammonium nitrate aqueous solution, wherein the concentration of ammonium ions is 0.1-2 mol/L; controlling the mass concentration of the ZK-5 molecular sieve to be 5 g/L-15 g/L in the ion exchange process; more preferably, the concentration of ammonium ions is 0.5-1.2 mol/L; the mass concentration of the ZK-5 molecular sieve is controlled to be 8 g/L-12 g/L in the ion exchange process.
The preferred ammonium ion concentration and molecular sieve mass concentration can ensure the exchange efficiency and substitution degree of the ammonium ions and active sites in the ZK-5 molecular sieve while saving cost, lay a foundation for the copper ion exchange in the step 2, and improve the catalytic activity of the catalyst product.
Preferably, the copper salt solution in the step 2 is at least one of copper chloride, copper nitrate, copper sulfate or copper acetate, wherein the concentration of copper ions is 0.001-0.5 mol/L; the mass concentration of the H-ZK-5 molecular sieve is controlled to be 5-15 g/L in the ion exchange process, the more preferable copper ion concentration is 0.001-0.1 mol/L, and the mass concentration of the H-ZK-5 molecular sieve is controlled to be 8-12 g/L in the ion exchange process.
The optimized concentration of the copper ions and the concentration of the H-ZK-5 molecular sieve can save cost, ensure the exchange efficiency and the substitution degree of ammonium ions and active sites inside the ZK-5 molecular sieve, improve the catalytic activity of a catalyst product and avoid the inactivation of the catalyst.
Drawings
FIG. 1 is an XRD pattern of the ZK-5 molecular sieve obtained in example 1 of the present invention and comparative examples 1, 3 and 5;
FIG. 2 is a scanning electron micrograph of the ZK-5 molecular sieve obtained in example 1 of the present invention;
FIG. 3 shows NO conversion at different temperatures for ZK-5 molecular sieves of example 1 and comparative examples 1 and 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention is further illustrated below in the following examples. Wherein the ZK-5 seed crystals used in each example were prepared by the following method.
Step a: dissolving potassium hydroxide in deionized water, adding aluminum hydroxide after KOH is completely dissolved, and stirring until a clear solution A is obtained, wherein the mass ratio of potassium hydroxide to aluminum hydroxide is 3: 1.
step b: and (B) sequentially dissolving strontium nitrate and 18-crown ether-6 in deionized water, dropwise adding colloidal silica into the solution under the condition of vigorous stirring, and continuously stirring for 1h to obtain a solution B, wherein the ratio of the quantity of silicon elements in the strontium nitrate, the 18-crown ether-6 and the colloidal silica to the quantity of the aluminum hydroxide in the step a is strontium nitrate: 18-crown-6: silicon element in colloidal silica: 1-aluminum hydroxide: 2: 20: 4. the ratio of the total amount of water used in step a and step b to the amount of aluminum hydroxide species is 400: 1.
step c: adding the cooled solution A into the solution B, and continuously stirring until the mixture is gelatinous. Transferring the obtained gel into a hydrothermal reaction kettle to react for 5d at 150 ℃. Washing, drying and calcining the obtained product to obtain the ZK-5 crystal seed.
Example 1
The embodiment provides a ZK-5 molecular sieve, and the preparation method of the ZK-5 molecular sieve specifically comprises the following steps:
s1: dissolving 0.46mol of KOH in deionized water, and adding 0.2mol of Al (OH) after the KOH is completely dissolved3Heating to 100 ℃, and continuing stirring until a clear solution A is obtained;
s2: sequentially dissolving 0.01mol of strontium nitrate and ZK-5 seed crystal in deionized water, stirring for 10min, adding silica sol containing 1mol of Si element under vigorous stirring, and then adding 0.04mol of H2O2Stirring is continued for 30min to obtain gel B. Wherein the mass of the ZK-5 seed crystal is 1.53g, which is equivalent to the aluminum element in the aluminum hydroxide and is Al2O3Measured on Al2O315% of the total mass of (1) and (2), the total amount of water used in step (1) and step (2) is 16 mol;
s3: and dropwise adding the clear solution A cooled to room temperature into the gel B, continuously stirring for 1h, transferring to a hydrothermal reaction kettle, standing for reaction and crystallization for 3.5d at 150 ℃, washing the obtained product, drying for 12h at 80 ℃, and calcining for 6h at 560 ℃ to obtain the ZK-5 molecular sieve.
Example 2
This example provides a process for preparing a Cu-ZK-5 molecular sieve catalyst using the ZK-5 molecular sieve obtained in example 1. The method specifically comprises the following steps:
step 1: adding 2g of the ZK-5 molecular sieve obtained in the example 1 and 10.7g of ammonium chloride into 200ml of deionized water, stirring for 10 hours at 80 ℃, centrifuging, drying, and repeating for 2 times to obtain an H-ZK-5 molecular sieve;
and 2, step: and (2) adding 2g of the H-ZK-5 molecular sieve obtained in the step (1) and 0.4g of copper acetate into 200ml of deionized water, stirring for 1H at 80 ℃, washing, drying, and roasting for 4H at 550 ℃ to obtain the Cu-ZK-5 molecular sieve catalyst.
Example 3
The embodiment provides a ZK-5 molecular sieve, and the preparation method of the ZK-5 molecular sieve specifically comprises the following steps:
s1: dissolving 0.46mol of KOH in deionized water, and adding 0.2mol of Al (OH) after the KOH is completely dissolved3Heating to 100 ℃, and continuing stirring until a clear solution A is obtained;
s2: dissolving 0.01mol of strontium nitrate and ZK-5 seed crystal in deionized water in sequence, stirring for 10min, adding water glass containing 1mol of Si element under vigorous stirring, and then adding 0.04mol of H2O2Continuously stirring for 30min to obtain gel B, wherein the mass of the ZK-5 seed crystal is 1.53g, which is equivalent to that of aluminum element in aluminum hydroxide and Al2O3Measured on Al2O315% of the total mass of (1) and (2), the total amount of water used in step (1) and step (2) is 16 mol;
s3: and dropwise adding the clear solution A cooled to room temperature into the gel B, continuously stirring for 1h, transferring to a hydrothermal reaction kettle, standing at 150 ℃ for reaction, crystallizing for 3d, washing the obtained product, drying at 80 ℃ for 12h, and calcining at 560 ℃ for 6h to obtain the ZK-5 molecular sieve.
Example 4
This example provides a process for preparing a Cu-ZK-5 molecular sieve catalyst using the ZK-5 molecular sieve obtained in example 3. The method specifically comprises the following steps:
step 1: adding 2g of the ZK-5 molecular sieve obtained in the example 3 and 16g of ammonium nitrate into 200ml of deionized water, stirring for 10 hours at 80 ℃, centrifuging, drying, and repeating for 2 times to obtain an H-ZK-5 molecular sieve;
step 2: and (2) adding 2g of the H-ZK-5 molecular sieve obtained in the step (1) and 0.26g of copper chloride into 200ml of deionized water, stirring for 1H at 80 ℃, washing, drying, and roasting for 4H at 550 ℃ to obtain the Cu-ZK-5 molecular sieve catalyst.
Example 5
The embodiment provides a ZK-5 molecular sieve, and the preparation method of the ZK-5 molecular sieve specifically comprises the following steps:
s1: dissolving 0.46mol of KOH in deionized water, and adding 0.2mol of Al (OH) after the KOH is completely dissolved3Heating to 100 ℃, and continuing stirring until a clear solution A is obtained;
s2: sequentially dissolving 0.01mol of strontium nitrate and ZK-5 seed crystal in deionized water, stirring for 10min, adding fumed silica containing 1mol of Si element under vigorous stirring, and adding 0.05mol of H2O2Continuously stirring for 30min to obtain gel B, wherein the mass of the ZK-5 seed crystal is 1.53g, which is equivalent to that of aluminum element in aluminum hydroxide and Al2O3Measured on Al2O315% of the total mass of (1) and (2), the total amount of water used in step (1) and step (2) is 16 mol;
s3: and dropwise adding the clear solution A cooled to room temperature into the gel B, continuously stirring for 1h, transferring to a hydrothermal reaction kettle, standing at 150 ℃, reacting, crystallizing for 3d, washing the obtained product, drying at 80 ℃ for 12h, and calcining at 560 ℃ for 6h to obtain the ZK-5 molecular sieve.
Example 6
This example provides a process for preparing a Cu-ZK-5 molecular sieve catalyst using the ZK-5 molecular sieve obtained in example 5. The method specifically comprises the following steps:
step 1: adding 2g of the ZK-5 molecular sieve obtained in the example 5 and 13.2g of ammonium sulfate into 200ml of deionized water, stirring for 10 hours at 80 ℃, centrifuging, drying, and repeating for 2 times to obtain an H-ZK-5 molecular sieve;
step 2: and (2) adding 2g of the H-ZK-5 molecular sieve obtained in the step (1) and 0.12g of copper nitrate into 200ml of deionized water, stirring for 1H at 80 ℃, washing, drying, and roasting for 4H at 550 ℃ to obtain the Cu-ZK-5 molecular sieve catalyst.
Example 7
The embodiment provides a ZK-5 molecular sieve, and the preparation method of the ZK-5 molecular sieve specifically comprises the following steps:
s1: dissolving 0.46mol of KOH in deionized water, and adding 0.2mol of Al (OH) after the KOH is completely dissolved3Heating to 100 ℃, and continuing stirring until a clear solution A is obtained;
s2: sequentially dissolving 0.01mol of strontium nitrate and ZK-5 seed crystal in deionized water, stirring for 10min, adding white carbon black containing 1mol of Si element under the condition of vigorous stirring, and then adding 0.04mol of H2O2Continuously stirring for 30min to obtain gel B, wherein the mass of the ZK-5 seed crystal is 1.53g, which is equivalent to that of aluminum element in aluminum hydroxide and Al2O3Measured on Al2O315% of the total mass of (1) and (2), the total amount of water used in step (1) and step (2) is 16 mol;
s3: and dropwise adding the clear solution A cooled to room temperature into the gel B, continuously stirring for 1h, transferring to a hydrothermal reaction kettle, standing for reaction and crystallization for 3.5d at 150 ℃, washing the obtained product, drying for 12h at 80 ℃, and calcining for 6h at 560 ℃ to obtain the ZK-5 molecular sieve.
Example 8
This example provides a process for preparing a Cu-ZK-5 molecular sieve catalyst using the ZK-5 molecular sieve obtained in example 7: the method specifically comprises the following steps:
step 1: adding 2g of the ZK-5 molecular sieve obtained in the example 7 and 15.5g of ammonium acetate into 200ml of deionized water, stirring for 10 hours at 80 ℃, centrifuging, drying, and repeating for 2 times to obtain an H-ZK-5 molecular sieve;
step 2: and (2) adding 2g of the H-ZK-5 molecular sieve obtained in the step (1) and 0.31g of copper sulfate into 200ml of deionized water, stirring for 1H at 80 ℃, washing, drying, and roasting for 4H at 550 ℃ to obtain the Cu-ZK-5 molecular sieve catalyst.
Comparative example 1
Compared with the preparation method of the ZK-5 molecular sieve in the example 1, the preparation method of the ZK-5 molecular sieve keeps the same steps and process parameters as the preparation method of the example 1 except that the standing reaction crystallization time in S3 is 2 d.
Comparative example 2
This comparative example provides a method for preparing a Cu-ZK-5 molecular sieve catalyst using the ZK-5 molecular sieve obtained in comparative example 1. The specific processing and operating steps of the method remain the same as in example 2.
Comparative example 3
This comparative example provides a ZK-5 molecular sieve, which was prepared by a method similar to that of example 1 except that H was not added to S22O2In addition, the remaining steps and process parameters were in accordance with example 1.
Comparative example 4
This comparative example provides a method for preparing a Cu-ZK-5 molecular sieve catalyst using the ZK-5 molecular sieve obtained in comparative example 3. The specific processing and operating steps of the method remain the same as in example 2.
Comparative example 5
This comparative example provides a ZK-5 molecular sieve, the preparation of which is comparable to example 1 except that H is added to S22O2Except for the amount of 0.1mol, the remaining steps and process parameters were in accordance with example 1.
Comparative example 6
This comparative example provides a method for preparing a Cu-ZK-5 molecular sieve catalyst using the ZK-5 molecular sieve obtained in comparative example 5. The specific processing and operating steps of the method remain the same as in example 2.
Comparative example 7
This comparative example provides a method of preparing a Cu-ZK-5 molecular sieve catalyst using the ZK-5 molecular sieve obtained in example 1:
compared with the preparation method of the catalyst in the embodiment 2, the preparation method of the catalyst has the advantages that the steps and the process parameters are consistent with the embodiment 2 except that the mass of the copper acetate used in the step 2 is 0.2 g.
Comparative example 8
This comparative example provides a method of preparing a Cu-ZK-5 molecular sieve catalyst using the ZK-5 molecular sieve obtained in example 1:
compared with the preparation method of the catalyst in the example 2, the preparation method of the catalyst has the advantages that the steps and the process parameters are kept consistent with the example 2 except that the mass of the copper acetate used in the step 2 is 0.8 g.
Example of detection
(1) XRD pattern analysis was performed on the ZK-5 molecular sieves prepared in examples 1, 3, 5, 7, comparative example 1, comparative example 2 and comparative example 3, and the results are shown in FIG. 1, wherein the results for the ZK-5 molecular sieve catalysts of examples 1, 3, 5, 7 were close, providing only the XRD pattern of example 1.
As can be seen from fig. 1: the diffraction peak intensities of the ZK-5 molecular sieves prepared in comparative examples 1, 3, and 5 are all weaker than the molecular sieve prepared in example 1, indicating that the molecular sieves prepared in comparative examples 1, 3, and 5 have a lower crystallinity than the ZK-5 molecular sieve prepared in example 1.
(2) The microstructures of the ZK-5 molecular sieves prepared in examples 1, 3, 5 and 7 were observed by scanning electron microscopy, wherein the scanning electron microscopy of the ZK-5 molecular sieve prepared in example 1 is shown in FIG. 2, and the results of the observation of examples 3, 5 and 7 are close to those of example 1.
(3) The catalytic activity of the Cu-ZK-5 molecular sieve catalysts prepared in the examples 2, 4, 6 and 8 and the comparative examples 2, 4, 6, 7 and 8 is detected, and the specific scheme is as follows:
a0.13 g sample of the catalyst was added to a quartz glass tube with a simulated flue gas composition of 500ppm NH3500ppm NO, 10% O2，N2Is the balance gas. The total flow of the reaction gas is 300mL/min, and the space velocity is 100,000h-1The reaction temperature is 100-550 ℃. The catalytic performance of each Cu-ZK-5 catalyst is respectively tested, and the obtained activity data are shown in table 1; the catalytic conversion curves for the molecular sieve catalysts prepared in example 2, comparative example 2 and comparative example 4 are shown in fig. 3.
TABLE 1
| Conversion at 150 ℃ C | 350 ℃ conversion rate | Conversion rate at 500 DEG C | |
| Example 2 | 95％ | 99％ | 93％ |
| Example 4 | 90％ | 99％ | 88％ |
| Example 6 | 92％ | 99％ | 92％ |
| Example 8 | 95％ | 99％ | 94％ |
| Comparative example 2 | 52％ | 90％ | 79％ |
| Comparative example 4 | 46％ | 88％ | 70％ |
| Comparative example 6 | 42％ | 99％ | 90％ |
| Comparative example 7 | 85％ | 99％ | 85％ |
| Comparative example 8 | 5％ | 23％ | 14％ |
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of a ZK-5 molecular sieve is characterized by comprising the following steps:
s1: dissolving a soluble aluminum source and an alkali metal compound in water to obtain a clear solution;
s2: uniformly mixing a silicon source, strontium nitrate, ZK-5 seed crystal, water and hydrogen peroxide to prepare gel;
s3: and dropwise adding the clarified solution into the gel, uniformly mixing, standing for crystallization, and washing, drying and calcining the obtained product to obtain the ZK-5 molecular sieve.
2. The method of claim 1, wherein the aluminum source in S1 is a soluble salt or base containing aluminum; and/or
The alkali metal compound is soluble salt or alkali containing potassium element.
3. The method of claim 2, wherein the aluminum in the source of S1 is Al2O3The potassium element in the solid alkali metal compound is calculated as K2Calculated as O, Al2O3And K2The mass ratio of O is 1: 2 to 2.5.
4. The method of claim 1, wherein the silicon source in S2 is at least one of water glass, silica sol, sodium silicate, fumed silica, and silica white.
5. The method for preparing ZK-5 molecular sieve of claim 1, wherein the silicon element in the silicon source in S2 is SiO2Calculated by strontium nitrate (SrO), and the aluminum element in the aluminum source of S1 is Al2O3Counting:
the ratio of the aluminum source in S1 to the silicon source, strontium nitrate and hydrogen peroxide in S2 is Al2O3：SiO2：SrO：H2O21: 9-11: 0.08-0.12: 0.2 to 0.6; and/or
The mass ratio of the aluminum source in S1 to the ZK-5 seed crystal in S2 is 100: 5-30; and/or
The ratio of the total amount of water used in S1 and S2 to the amount of aluminum source in S1 is 150-170: 1.
6. the method for preparing the ZK-5 molecular sieve of claim 1, wherein the crystallization temperature in the crystallization process of S3 is 130-180 ℃, and the crystallization time is 2.5-3.5 days.
7. A ZK-5 molecular sieve, characterized in that it is prepared by the method of any one of claims 1 to 6.
8. Use of the ZK-5 molecular sieve of claim 7 in the preparation of a Cu-ZK-5 molecular sieve catalyst.
9. A preparation method of a Cu-ZK-5 molecular sieve catalyst is characterized by being prepared by the ZK-5 molecular sieve of claim 7, and specifically comprising the following steps:
step 1: mixing the ZK-5 molecular sieve with an ammonium salt solution, performing ion exchange, washing and drying, and repeating for 2-3 times to obtain an H-ZK-5 molecular sieve;
step 2: and mixing the H-ZK-5 molecular sieve with a copper salt solution, performing ion exchange, washing, drying and roasting to obtain the Cu-ZK-5 molecular sieve catalyst.
10. The method for preparing the Cu-ZK-5 molecular sieve catalyst according to claim 9, wherein the ammonium ion concentration in the ammonium salt solution in step 1 is 0.1-2 mol/L, and the mass concentration of the ZK-5 molecular sieve is controlled to be 5-15 g/L in the ion exchange process; in the step 2, the concentration of copper ions in the copper salt solution is 0.001-0.5 mol/L, and the mass concentration of the H-ZK-5 molecular sieve is controlled to be 5-15 g/L in the ion exchange process.
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