Cu(i) / 4a molecular sieve adsorbent, method of making and use thereof

Abstract

The application discloses a Cu(I) / 4A molecular sieve adsorbent and a preparation method and application thereof, and relates to the technical field of adsorbents, in particular to a Cu(I) / 4A molecular sieve adsorbent and a preparation method and application thereof. The preparation method comprises the following steps: sequentially mixing a copper salt, an organic amine, sodium hydroxide, deionized water, an aluminum source and a silicon source, then performing a crystallization reaction, and finally performing a reduction reaction with a reducing agent, so as to prepare the Cu(I) / 4A molecular sieve adsorbent. The complex formed by the copper salt and the organic amine is loaded into the framework of the 4A molecular sieve, so that the Cu(I) / 4A molecular sieve adsorbent is prepared. The method has the advantages of low cost, simple process, environmental friendliness and the like. Further, the Cu(I) / 4A molecular sieve adsorbent provides a pi complexation effect for the monovalent copper ions which are more uniformly loaded on the surface and in the pores, so that the adsorption capacity of carbon monoxide is greatly improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of adsorbents, and particularly relates to a Cu(I) / 4A molecular sieve adsorbent and a preparation method and application thereof. BACKGROUND

[0002] The contradiction between the increasing demand for energy and environmental pollution has become a global hot issue at the present stage. The combustion of fossil energy will produce a large amount of pollutants, causing environmental pollution. Fuel oil is a widely used fossil energy, and hydrogen is considered to be the most important clean and renewable energy for the future of sustainable energy. However, there are still great difficulties in the efficient use of hydrogen. In industry, hydrogen is produced by methane reforming, and methanol is considered to be one of the most promising hydrogen production technologies for hydrogen fuel cells. However, the hydrogen produced by this method often contains carbon monoxide impurities, and a small amount of CO will poison the catalyst in the fuel cell, thereby affecting the normal operation of the cell. In particular, for hydrogen fuel cells with platinum-based catalysts, the content of CO must be as low as 0.2 ppm, so the hydrogen produced by methanol reforming must be purified.

[0003] Adsorption separation is a method of realizing efficient separation by using the adsorption capacity and selectivity difference of adsorbents for different gas components, and through the adsorption enrichment and desorption of the adsorption bed. According to different desorption regeneration methods, it can be divided into temperature swing adsorption (TSA) and pressure swing adsorption (PSA). Temperature swing adsorption is based on the difference in adsorption capacity of adsorbents at different temperatures to realize regeneration and separation, and pressure swing adsorption is based on the difference in adsorption capacity of adsorbents at different pressures to realize regeneration and separation. Obviously, the heating-cooling process through temperature swing is extremely energy-consuming, and compared with it, the regeneration rate of PSA process is faster, the energy consumption is lower, the equipment is simple, the degree of automation is high, and it is easy to large-scale industrial production. At present, there are many types of adsorbents, such as porous carbon, porous organic polymers, and metal-organic frameworks, which are being widely studied and have obvious performance effects. Therefore, adsorption separation technology is expected to replace cryogenic separation technology in the near future.

[0004] Chinese patent CN1103816 discloses a method for preparing a zeolite adsorbent with high selectivity for adsorbing carbon monoxide. Copper ions are loaded on NaY zeolite by ion exchange and impregnation. The adsorption capacity of the prepared adsorbent for carbon monoxide at 50°C is 2.57 mmol / g. Chinese patent CN104190364A discloses a low-toxicity method for preparing MIL-100(Fe) crystals with high adsorption capacity for CO. Sodium fluoride is used as a reaction aid instead of the toxic substance hydrofluoric acid, which reduces the toxicity of the prepared MIL-100(Fe) crystal material. The obtained MIL-100(Fe) crystal material has a high working adsorption capacity for CO. Chinese patent CN106315613A discloses a new 13X type molecular sieve for CO adsorption, a preparation method and application thereof. The prepared adsorbent has high CO selectivity, CO yield and CO cyclic regeneration capacity. The preparation process is simple, and the preparation and use costs of the adsorbent are effectively reduced. Chinese patent CN112705180A discloses a method for preparing an adsorbent for CO pressure swing adsorption. The modified carrier is treated by gas-solid phase treatment with an organic amine, and then mixed with a copper source and formed into a shape to prepare an adsorbent precursor. The problems of low mechanical strength and low CO adsorption efficiency of conventional adsorbents are solved.

[0005] In summary, although some methods for preparing adsorbents for adsorbing carbon monoxide are disclosed in the prior art, the existing adsorbents have the following problems: a. The existing methods for loading copper ions, such as impregnation, double solvent method and thermal dispersion method, have a complex preparation process. A large amount of waste liquid is generated during the preparation process, and the preparation process needs to be carried out in a harsh preparation environment such as inert gas or vacuum environment; b. The metal organic framework as the carrier of the adsorbent has poor thermal stability. The framework collapses and loses the ability to adsorb CO when the temperature is higher than 300°C; c. The dispersion degree of copper ions is low, and the regeneration performance of the adsorbent is poor. SUMMARY

[0006] The present application aims to at least partially solve one of the problems in the related art. In view of the problems of low adsorption capacity, low adsorption rate, low adsorption selectivity and complex preparation of the existing CO adsorbents, a Cu(I) / 4A molecular sieve adsorbent is proposed. The new carbon monoxide adsorbent has the advantages of large CO adsorption capacity, high CO / H2 selectivity and simple preparation method.

[0007] In one aspect of the present application, a method for preparing a Cu(I) / 4A molecular sieve adsorbent is proposed. According to an embodiment of the present application, the method comprises:

[0008] (1) stirring and mixing copper salt and organic amine to obtain a first mixture;

[0009] (2) adding sodium hydroxide and deionized water into the first mixture slowly for second stirring and mixing to obtain a second mixture;

[0010] (3) adding an aluminum source into the second mixture for third stirring and mixing to obtain a third mixture;

[0011] (4) adding a silicon source into the third mixture for fourth stirring and mixing to obtain a fourth mixture;

[0012] (5) performing a crystallization reaction on the fourth mixture, and after cooling to room temperature, performing filtration, washing and first drying to obtain a Cu(I) / 4A molecular sieve adsorbent precursor;

[0013] (6) performing a reduction reaction on the Cu(I) / 4A molecular sieve adsorbent precursor and a reducing agent, and after cooling to room temperature, performing filtration, washing and second drying to obtain a Cu(I) / 4A molecular sieve adsorbent.

[0014] In some embodiments of the present application, the mass ratio of the copper salt, the organic amine, the sodium hydroxide, the deionized water, the aluminum source, the silicon source, the reducing agent is (0.1-0.5):(15-30):(0.1-0.3):(3-5):(0.5-3):(0.5-3):(0.05-0.1).

[0015] In some embodiments of the present application, in step (1), the copper salt comprises one or more of copper nitrate, copper sulfate and copper chloride.

[0016] In some embodiments of the present application, in step (1), the organic amine comprises tetramethylammonium hydroxide.

[0017] In some embodiments of the present application, in step (1), the first stirring and mixing comprises stirring at room temperature for 10-30 min.

[0018] In some embodiments of the present application, in step (2), the second stirring and mixing comprises stirring at room temperature for 10-30 min.

[0019] In some embodiments of the present application, in step (3), the aluminum source comprises one or more of aluminum isopropoxide and aluminum hydroxide.

[0020] In some embodiments of the present application, in step (3), the third stirring and mixing comprises stirring at room temperature for 10-30 min.

[0021] In some embodiments of the present application, in step (4), the silicon source comprises one or more of tetraethyl orthosilicate, fumed silica or silica sol.

[0022] In some embodiments of the application, in step (4), the fourth stirring mixing comprises: stirring for 10-30 min at room temperature.

[0023] In some embodiments of the application, in step (5), the crystallization reaction comprises: loading the fourth mixture into a polytetrafluoroethylene reaction kettle, and crystallizing for 3-5 h at 100-200℃.

[0024] In some embodiments of the application, in step (6), the reducing reaction comprises: mixing and grinding the Cu(I) / 4A molecular sieve adsorbent precursor with the reducing agent, and heating for 4 h under a nitrogen atmosphere at 100-200℃.

[0025] In some embodiments of the application, in step (6), the reducing agent comprises one or more of VCl3 or sodium sulfite.

[0026] In some embodiments of the application, in step (6), the second drying temperature is 80-120℃, and the drying time is 8-16 h.

[0027] In a second aspect of the application, the application provides a Cu(I) / 4A molecular sieve adsorbent. According to embodiments of the application, the Cu(I) / 4A molecular sieve adsorbent is prepared by the method described above.

[0028] In a third aspect of the application, the application provides a use of a Cu(I) / 4A molecular sieve adsorbent. According to embodiments of the application, the Cu(I) / 4A molecular sieve adsorbent is used for adsorbing and separating carbon monoxide.

[0029] Further, before use, the Cu(I) / 4A molecular sieve adsorbent is treated in a vacuum oven at 80-120℃ for 8-10 h; at a temperature of 20-40℃ and under a pressure of 0-1000 mbar, 0.2-0.4 MPa carbon monoxide gas is adsorbed by an IGA intelligent gravimetric analyzer loaded with the Cu(I) / 4A molecular sieve adsorbent, and the IGA intelligent gravimetric analyzer is used to detect the adsorption amount of carbon monoxide and to test the regeneration performance; the regeneration test conditions are 100℃ vacuum treatment for 4 h.

[0030] The Cu(I) / 4A molecular sieve adsorbent prepared by the application has the following advantages compared with the prior art:

[0031] (1) The existing preparation method of pi complex adsorbent is mostly thermal dispersion method, which cannot load copper ions uniformly in the molecular sieve channel and cannot control the loading amount of Cu. The complex formed by the copper source and the organic amine is used to load the copper component into the molecular sieve skeleton, and the Cu(I) / 4A molecular sieve adsorbent is prepared, which has the advantages of low cost, simple process, environmental friendliness, etc. and can be used for carbon monoxide adsorption evaluation.

[0032] (2) Compared with the ordinary impregnation method and the double solvent method for adsorbing carbon monoxide, the Cu(I) / 4A molecular sieve adsorbent has more uniform monovalent copper ions on the surface and in the channel to provide pi complexation, which greatly improves the adsorption capacity.

[0033] In summary, the Cu(I) / 4A molecular sieve adsorbent of the present application uses the complex formed by the copper salt and the organic amine as a template agent to synthesize the Cu(I) / 4A molecular sieve adsorbent, solves the harsh problem in the process of loading copper ions, and has the advantages of high activity, high stability, high regeneration, high adsorption capacity and environmental friendliness. The Cu(I) / 4A molecular sieve adsorbent of the present application has good adsorption effect in the operation of carbon monoxide adsorption and separation.

[0034] Additional aspects and advantages of the present application will be in part apparent and in part pointed out hereinafter in the description of embodiments. BRIEF DESCRIPTION OF DRAWINGS

[0035] The above and / or additional aspects and advantages of the present application will become apparent and be readily appreciated from the following description of embodiments, taken in conjunction with the accompanying drawings.

[0036] Figure 1 The carbon monoxide isothermal adsorption test graph of the Cu(I) / 4A molecular sieve adsorbent of Examples 1-5;

[0037] Figure 2 The carbon monoxide isothermal adsorption test graph of the Cu(I) / 4A molecular sieve adsorbent of Comparative Examples 1-7;

[0038] Figure 3 The carbon monoxide regeneration performance test graph of the Cu(I) / 4A molecular sieve adsorbent of Example 3;

[0039] Figure 4 The carbon monoxide regeneration performance test graph of the Cu(I) / 4A molecular sieve adsorbent of Example 8;

[0040] Figure 5 The carbon monoxide regeneration performance test graph of the Cu(I) / 4A molecular sieve adsorbent of Comparative Example 5. DETAILED DESCRIPTION

[0041] Embodiments of the present application are described in detail below with reference to the attached drawing figures, wherein like reference numerals refer to like elements throughout. The embodiments described below are exemplary in nature, and are intended to be illustrative of the present application rather than to limit the same.

[0042] The present application is described herein with reference to particular embodiments for purposes of description, but the application can be practiced apart from those specific embodiments.

[0043] Example 1

[0044] 0.1 g of copper nitrate was mixed with 25 g of tetramethylammonium hydroxide and stirred at room temperature for 30 min to form a complex. 0.2 g of sodium hydroxide and 4 g of deionized water were slowly added to the complex and stirred at room temperature for 10 min. 2 g of aluminum isopropoxide was added to the complex and stirred at room temperature for 30 min to form a gel. 2 g of tetraethyl orthosilicate was added to the complex and stirred at room temperature for 30 min. The resulting mixture was loaded into a polytetrafluoroethylene reactor and crystallized at 100 °C for 4 h and cooled to room temperature. The mixture was filtered, washed, and dried to obtain a Cu(l) / 4A molecular sieve adsorbent precursor. The Cu(l) / 4A molecular sieve adsorbent precursor was mixed with 0.1 g of VCl3and ground. The mixture was heat treated at 200 °C under a nitrogen atmosphere for 4 h, cooled to room temperature, and filtered, washed, and dried to obtain a Cu(l) / 4A molecular sieve adsorbent.

[0045] The Cu(l) / 4A molecular sieve adsorbent was used to perform carbon monoxide adsorption tests on an IGA smart gravimetric analyzer. The purity of the carbon monoxide in the gas was 99.9%. The adsorbent activity test experimental conditions were as follows: the temperature was 25 °C, the pressure range was 0-1000 mbar, the IGA smart gravimetric analyzer was loaded with the Cu(l) / 4A molecular sieve adsorbent, and the adsorption test was performed to detect the mass change in the sample tube. The test results of the Cu(l) / 4A molecular sieve adsorbent are shown in Table 1. Figure 1 The regeneration performance of Example 1 was tested. The Cu(l) / 4A molecular sieve adsorbent of Example 1, which had been subjected to carbon monoxide adsorption tests, was subjected to vacuum treatment at 100 °C for 4 h, and then subjected to carbon monoxide adsorption tests again. The purity of the carbon monoxide in the gas was 99.9%. The adsorbent activity test experimental conditions were as follows: the temperature was 25 °C, the pressure range was 0-1000 mbar, the IGA smart gravimetric analyzer was loaded with the regenerated Cu(l) / 4A molecular sieve adsorbent, and the adsorption test was performed to detect the mass change in the sample tube. The Cu(l) / 4A molecular sieve adsorbent was subjected to 5 regeneration tests.

[0046] Example 2

[0047] Cu(I) / 4A molecular sieve adsorbent precursor. The obtained Cu(I) / 4A molecular sieve adsorbent precursor was mixed with 0.1 g of VCl3and ground, and then vacuum heat-treated at 100°C for 4 h, and cooled to room temperature; filtered, washed, and dried to obtain a Cu(I) / 4A molecular sieve adsorbent.

[0048] Carbon monoxide adsorption tests were performed on the IGA smart gravimetric analyzer using the molecular sieve adsorbent of the present example. The purity of carbon monoxide in the gas was 99.9%, and the active test experimental conditions of the adsorbent were as follows: the IGA smart gravimetric analyzer was filled with the Cu(I) / 4A molecular sieve adsorbent, and the adsorption test was performed under the conditions of a temperature of 25°C and a pressure range of 0-1000 mbar, and the mass change in the sample tube was detected. The test results of the Cu(I) / 4A molecular sieve adsorbent are shown in Table 1. Figure 1 The regeneration performance test was performed on Example 2. The Cu(I) / 4A molecular sieve adsorbent of Example 2 after the carbon monoxide adsorption test was vacuum treated at 100°C for 4 h, and then the carbon monoxide adsorption test was performed again. The purity of carbon monoxide in the gas was 99.9%, and the active test experimental conditions of the regenerated adsorbent were as follows: the IGA smart gravimetric analyzer was filled with the regenerated Cu(I) / 4A molecular sieve adsorbent, and the adsorption test was performed under the conditions of a temperature of 25°C and a pressure range of 0-1000 mbar, and the mass change in the sample tube was detected. The Cu(I) / 4A molecular sieve adsorbent was subjected to 5 regeneration tests.

[0049] Example 3

[0050] Cu(I) / 4A molecular sieve adsorbent precursor. The Cu(I) / 4A molecular sieve adsorbent precursor was mixed with 0.1 g of VCl3and ground, and then heated under vacuum at 100 °C for 4 h and cooled to room temperature; filtered, washed, and dried to obtain a Cu(I) / 4A molecular sieve adsorbent.

[0051] Carbon monoxide adsorption tests were performed using the molecular sieve adsorbent of the present example on an IGA smart gravimetric analyzer. The purity of carbon monoxide in the gas was 99.9%, and the active test experimental conditions of the adsorbent were: the IGA smart gravimetric analyzer was loaded with the Cu(I) / 4A molecular sieve adsorbent and the adsorption test was performed under the conditions of a temperature of 25 °C and a pressure range of 0-1000 mbar, and the mass change in the sample tube was detected. The test results of the Cu(I) / 4A molecular sieve adsorbent are shown in Table 1. Figure 1 The regeneration performance test was performed on Example 3. The Cu(I) / 4A molecular sieve adsorbent of Example 3 after the carbon monoxide adsorption test was vacuum treated at 100 °C for 4 h, and then the carbon monoxide adsorption test was performed again. The purity of carbon monoxide in the gas was 99.9%, and the active test experimental conditions of the regenerated adsorbent were: the IGA smart gravimetric analyzer was loaded with the regenerated Cu(I) / 4A molecular sieve adsorbent and the adsorption test was performed under the conditions of a temperature of 25 °C and a pressure range of 0-1000 mbar, and the mass change in the sample tube was detected. The Cu(I) / 4A molecular sieve adsorbent was tested for regeneration for 5 times, and the test results are shown in Table 2. Figure 3

[0052] Example 4

[0053] ​Cu(I) / 4A molecular sieve adsorbent precursor. The Cu(I) / 4A molecular sieve adsorbent precursor was mixed with 0.1 g of VCl3and ground, and then heated under vacuum at 100 °C for 4 h and cooled to room temperature; filtered, washed, and dried to obtain a Cu(I) / 4A molecular sieve adsorbent.

[0054] Carbon monoxide adsorption tests were performed using the molecular sieve adsorbent of the present example on an IGA Smart Gravimetric Analyzer. The purity of carbon monoxide in the gas was 99.9%, and the active test experimental conditions of the adsorbent were: the temperature was 25 °C, the pressure range was 0-1000 mbar, and the IGA Smart Gravimetric Analyzer was filled with the Cu(I) / 4A molecular sieve adsorbent to perform the adsorption test, and the mass change in the sample tube was detected. The test results of the Cu(I) / 4A molecular sieve adsorbent are shown in Table 1. Table 1 Figure 1 The regeneration performance test was performed on Example 4. The Cu(I) / 4A molecular sieve adsorbent of Example 4 after the carbon monoxide adsorption test was vacuum treated at 100 °C for 4 h, and then the carbon monoxide adsorption test was performed again. The purity of carbon monoxide in the gas was 99.9%, and the active test experimental conditions of the regenerated adsorbent were: the temperature was 25 °C, the pressure range was 0-1000 mbar, and the IGA Smart Gravimetric Analyzer was filled with the regenerated Cu(I) / 4A molecular sieve adsorbent to perform the adsorption test, and the mass change in the sample tube was detected. The Cu(I) / 4A molecular sieve adsorbent was subjected to 5 regeneration tests.

[0055] Example 5

[0056] Cu(I) / 4A molecular sieve adsorbent precursor. The Cu(I) / 4A molecular sieve adsorbent precursor was mixed with 0.1 g of VCl3and ground, and then heated under vacuum at 100 °C for 4 h and cooled to room temperature; filtered, washed, and dried to obtain a Cu(I) / 4A molecular sieve adsorbent.

[0057] Carbon monoxide adsorption tests were performed using the molecular sieve adsorbent of the present example on an IGA Smart Gravimetric Analyzer. The purity of carbon monoxide in the gas was 99.9%, and the active test experimental conditions of the adsorbent were: the temperature was 25 °C, the pressure range was 0-1000 mbar, and the IGA Smart Gravimetric Analyzer was filled with the Cu(I) / 4A molecular sieve adsorbent to perform the adsorption test, and the mass change in the sample tube was detected. The test results of the Cu(I) / 4A molecular sieve adsorbent are shown in Table 1. Figure 1 The regeneration performance test was performed on Example 5. The Cu(I) / 4A molecular sieve adsorbent of Example 5 after the carbon monoxide adsorption test was vacuum treated at 100 °C for 4 h, and then the carbon monoxide adsorption test was performed again. The purity of carbon monoxide in the gas was 99.9%, and the active test experimental conditions of the regenerated adsorbent were: the temperature was 25 °C, the pressure range was 0-1000 mbar, and the IGA Smart Gravimetric Analyzer was filled with the regenerated Cu(I) / 4A molecular sieve adsorbent to perform the adsorption test, and the mass change in the sample tube was detected. The Cu(I) / 4A molecular sieve adsorbent was subjected to 5 regeneration tests.

[0058] Example 6

[0059] CuSO4(0.1 g) was mixed with tetramethylammonium hydroxide (25 g) and stirred for 30 min at room temperature to form a complex. NaOH (0.2 g) and deionized water (4 g) were added slowly and stirred for 10 min at room temperature. Al(iPr)3(2 g) was added and stirred for 30 min at room temperature to form a gel. Tetraethyl orthosilicate (2 g) was added and stirred for 30 min at room temperature. The resulting mixture was loaded into a Teflon® reactor and heated at 200 °C under nitrogen for 4 h, cooled to room temperature, filtered, washed, and dried to obtain a Cu(I) / 4A molecular sieve adsorbent precursor. The Cu(I) / 4A molecular sieve adsorbent precursor was mixed with VCl3(0.1 g) and ground, and heated under vacuum at 100 °C for 4 h, cooled to room temperature, filtered, washed, and dried to obtain a Cu(I) / 4A molecular sieve adsorbent.

[0060] Carbon monoxide adsorption tests were performed using the molecular sieve adsorbents of the present examples on an IGA Smart Gravimetric Analyzer. The purity of the carbon monoxide in the gas was 99.9%, and the active test experimental conditions for the adsorbents were: temperature of 25 °C, pressure range of 0-1000 mbar, and the IGA Smart Gravimetric Analyzer was loaded with the Cu(I) / 4A molecular sieve adsorbent and the mass change in the sample tube was detected. Regeneration performance tests were performed on Example 6, and the Cu(I) / 4A molecular sieve adsorbent of Example 6 that had been tested for carbon monoxide adsorption was treated under vacuum at 100 °C for 4 h, and then tested again for carbon monoxide adsorption. The purity of the carbon monoxide in the gas was 99.9%, and the active test experimental conditions for the regenerated adsorbent were: temperature of 25 °C, pressure range of 0-1000 mbar, and the IGA Smart Gravimetric Analyzer was loaded with the regenerated Cu(I) / 4A molecular sieve adsorbent and the mass change in the sample tube was detected. The Cu(I) / 4A molecular sieve adsorbent was tested for regeneration 5 times.

[0061] Examples 7-10

[0062] Cu(I) / 4A molecular sieve adsorbents were prepared according to the steps and conditions of Example 6, and adsorption tests were performed. Only the amount of copper sulfate added was changed; the modified conditions are listed in Table 1. The adsorption test conditions were: temperature 25°C, pressure range 0–1000 mbar, and adsorption tests were performed using an IGA intelligent thermogravimetric analyzer filled with Cu(I) / 4A molecular sieve adsorbents, and the mass change in the sample tube was detected. Regeneration performance tests were performed on Examples 7–10. The Cu(I) / 4A molecular sieve adsorbents of Examples 7–10, after undergoing carbon monoxide adsorption tests, were subjected to vacuum treatment at 100°C for 4 hours, and carbon monoxide adsorption tests were performed again. The purity of carbon monoxide in the gas was 99.9%. The activity test conditions for the regenerated adsorbents were: temperature 25°C, pressure range 0–1000 mbar, and adsorption tests were performed using an IGA intelligent gravimetric analyzer filled with regenerated Cu(I) / 4A molecular sieve adsorbents, and the mass change in the sample tube was detected. Five regeneration tests were conducted on the Cu(I) / 4A molecular sieve adsorbent. The regeneration test results of Example 8 were... Figure 4 The information is provided in the text.

[0063] Example 11

[0064] 0.1 g of copper chloride and 25 g of tetramethylammonium hydroxide were mixed evenly and stirred at room temperature for 30 min to form a complex. Then, 0.2 g of sodium hydroxide and 4 g of deionized water were slowly added and stirred at room temperature for 10 min. 2 g of aluminum isopropoxide was added and stirred at room temperature for 30 min until a gel formed. 2 g of tetraethyl orthosilicate was added and stirred at room temperature for 30 min. The resulting mixture was placed in a polytetrafluoroethylene reactor and heated at 200 °C under a nitrogen atmosphere for 4 h, then cooled to room temperature; filtered, washed, and dried to obtain the Cu(I) / 4A molecular sieve adsorbent precursor. The obtained Cu(I) / 4A molecular sieve adsorbent precursor was mixed with 0.1 g of VCl3 and ground, then heated under vacuum at 100 °C for 4 h, then cooled to room temperature; filtered, washed, and dried to obtain the Cu(I) / 4A molecular sieve adsorbent.

[0065] Carbon monoxide adsorption was tested using the molecular sieve adsorption method described in this embodiment on an IGA intelligent gravimetric analyzer. The purity of carbon monoxide in the gas was 99.9%. The adsorbent activity test conditions were: temperature 25°C, pressure range 0–1000 mbar. The adsorption test was conducted on an IGA intelligent gravimetric analyzer filled with Cu(I) / 4A molecular sieve adsorbent, and the mass change in the sample tube was detected. Regeneration performance was tested for Example 11. The Cu(I) / 4A molecular sieve adsorbent of Example 11, after undergoing the carbon monoxide adsorption test, was subjected to vacuum treatment at 100°C for 4 hours, and then the carbon monoxide adsorption test was performed again. The purity of carbon monoxide in the gas was 99.9%. The regenerated adsorbent activity test conditions were: temperature 25°C, pressure range 0–1000 mbar. The adsorption test was conducted on an IGA intelligent gravimetric analyzer filled with regenerated Cu(I) / 4A molecular sieve adsorbent, and the mass change in the sample tube was detected. Five regeneration tests were conducted on the Cu(I) / 4A molecular sieve adsorbent.

[0066] Examples 12–15

[0067] Cu(I) / 4A molecular sieve adsorbents were prepared according to the steps and conditions of Example 11, and adsorption tests were performed. Only the amount of copper chloride added was changed; the modified conditions are listed in Table 1. The adsorption test conditions were: temperature 25°C, pressure range 0–1000 mbar, and adsorption tests were performed using an IGA intelligent thermogravimetric analyzer filled with Cu(I) / 4A molecular sieve adsorbents, detecting the mass change in the sample tube. Regeneration performance tests were performed on Examples 12–15. The Cu(I) / 4A molecular sieve adsorbents from Examples 12–15, after undergoing carbon monoxide adsorption tests, were subjected to vacuum treatment at 100°C for 4 hours, and carbon monoxide adsorption tests were performed again. The purity of carbon monoxide in the gas was 99.9%. The activity test conditions for the regenerated adsorbents were: temperature 25°C, pressure range 0–1000 mbar, and adsorption tests were performed using an IGA intelligent gravimetric analyzer filled with regenerated Cu(I) / 4A molecular sieve adsorbents, detecting the mass change in the sample tube. Five regeneration tests were conducted on the Cu(I) / 4A molecular sieve adsorbent.

[0068] Example 16

[0069] 0.3 g of copper nitrate and 25 g of tetramethylammonium hydroxide were mixed evenly and stirred at room temperature for 30 min to form a complex. Then, 0.2 g of sodium hydroxide and 4 g of deionized water were slowly added and stirred at room temperature for 10 min. 2 g of aluminum isopropoxide was added and stirred at room temperature for 30 min until a gel formed. 0.6 g of fumed silica was added and stirred at room temperature for 30 min. The resulting mixture was placed in a polytetrafluoroethylene reactor and crystallized at 100 °C for 4 h. After cooling to room temperature, the mixture was filtered, washed, and dried to obtain a Cu(I) / 4A molecular sieve adsorbent precursor. The obtained Cu(I) / 4A molecular sieve adsorbent precursor was mixed with 0.1 g of VCl3 and ground. The mixture was then heated at 200 °C under a nitrogen atmosphere for 4 h and cooled to room temperature. After filtering, washing, and drying, the Cu(I) / 4A molecular sieve adsorbent was obtained.

[0070] Carbon monoxide adsorption was tested using the molecular sieve adsorption method described in this embodiment on an IGA intelligent gravimetric analyzer. The purity of carbon monoxide in the gas was 99.9%. The adsorbent activity test conditions were: temperature 25°C, pressure range 0–1000 mbar. The adsorption test was conducted on an IGA intelligent gravimetric analyzer filled with Cu(I) / 4A molecular sieve adsorbent, and the mass change in the sample tube was detected. Regeneration performance was tested for Example 16. The Cu(I) / 4A molecular sieve adsorbent of Example 16, after undergoing the carbon monoxide adsorption test, was subjected to vacuum treatment at 100°C for 4 hours, and then the carbon monoxide adsorption test was performed again. The purity of carbon monoxide in the gas was 99.9%. The regenerated adsorbent activity test conditions were: temperature 25°C, pressure range 0–1000 mbar. The adsorption test was conducted on an IGA intelligent gravimetric analyzer filled with regenerated Cu(I) / 4A molecular sieve adsorbent, and the mass change in the sample tube was detected. Five regeneration tests were conducted on the Cu(I) / 4A molecular sieve adsorbent.

[0071] Example 17

[0072] 0.3 g of copper nitrate and 25 g of tetramethylammonium hydroxide were mixed evenly and stirred at room temperature for 30 min to form a complex. Then, 0.2 g of sodium hydroxide and 4 g of deionized water were slowly added and stirred at room temperature for 10 min. 2 g of aluminum isopropoxide was added and stirred at room temperature for 30 min until a gel formed. 0.84 g of silica sol was added and stirred at room temperature for 30 min. The resulting gel was placed in a polytetrafluoroethylene reactor and crystallized at 100 °C for 4 h, then cooled to room temperature; filtered, washed, and dried to obtain the Cu(I) / 4A molecular sieve adsorbent precursor. The obtained Cu(I) / 4A molecular sieve adsorbent precursor was mixed with 0.1 g of VCl3 and ground, then heated at 200 °C under a nitrogen atmosphere for 4 h, and cooled to room temperature; filtered, washed, and dried to obtain the Cu(I) / 4A molecular sieve adsorbent.

[0073] Carbon monoxide adsorption was tested using the molecular sieve adsorption method described in this embodiment on an IGA intelligent gravimetric analyzer. The purity of carbon monoxide in the gas was 99.9%. The adsorbent activity test conditions were: temperature 25°C, pressure range 0–1000 mbar. The adsorption test was conducted on an IGA intelligent gravimetric analyzer filled with Cu(I) / 4A molecular sieve adsorbent, and the mass change in the sample tube was detected. Regeneration performance was tested for Example 17. The Cu(I) / 4A molecular sieve adsorbent of Example 17, after undergoing the carbon monoxide adsorption test, was subjected to vacuum treatment at 100°C for 4 hours, and then the carbon monoxide adsorption test was performed again. The purity of carbon monoxide in the gas was 99.9%. The regenerated adsorbent activity test conditions were: temperature 25°C, pressure range 0–1000 mbar. The adsorption test was conducted on an IGA intelligent gravimetric analyzer filled with regenerated Cu(I) / 4A molecular sieve adsorbent, and the mass change in the sample tube was detected. Five regeneration tests were conducted on the Cu(I) / 4A molecular sieve adsorbent.

[0074] Example 18

[0075] 0.3 g of copper nitrate and 25 g of tetramethylammonium hydroxide were mixed evenly and stirred at room temperature for 30 min to form a complex. Then, 0.2 g of sodium hydroxide and 4 g of deionized water were slowly added to the mixture and stirred at room temperature for 10 min. 0.78 g of aluminum hydroxide was added and stirred at room temperature for 30 min until a gel-like consistency was formed. 2 g of tetraethyl orthosilicate was added and stirred at room temperature for 30 min. The resulting mixture was placed in a polytetrafluoroethylene reactor and heated at 200 °C under a nitrogen atmosphere for 4 h, then cooled to room temperature. The mixture was filtered, washed, and dried to obtain a Cu(I) / 4A molecular sieve adsorbent precursor. The obtained Cu(I) / 4A molecular sieve adsorbent precursor was mixed with 0.1 g of VCl3 and ground, then heated under vacuum at 100 °C for 4 h, and cooled to room temperature. The mixture was filtered, washed, and dried to obtain the Cu(I) / 4A molecular sieve adsorbent.

[0076] Carbon monoxide adsorption was tested using the molecular sieve adsorption described in this embodiment on an IGA intelligent gravimetric analyzer. The purity of carbon monoxide in the gas was 99.9%. The adsorbent activity test conditions were: temperature 25°C, pressure range 0–1000 mbar. The adsorption test was conducted on an IGA intelligent gravimetric analyzer filled with Cu(I) / 4A molecular sieve adsorbent, and the mass change in the sample tube was detected. Regeneration performance was tested for Example 18. The Cu(I) / 4A molecular sieve adsorbent of Example 18, after undergoing the carbon monoxide adsorption test, was subjected to vacuum treatment at 100°C for 4 hours, and then the carbon monoxide adsorption test was performed again. The purity of carbon monoxide in the gas was 99.9%. The regenerated adsorbent activity test conditions were: temperature 25°C, pressure range 0–1000 mbar. The adsorption test was conducted on an IGA intelligent gravimetric analyzer filled with regenerated Cu(I) / 4A molecular sieve adsorbent, and the mass change in the sample tube was detected. Five regeneration tests were conducted on the Cu(I) / 4A molecular sieve adsorbent.

[0077] Comparative Example 1

[0078] 0.2 g sodium hydroxide, 4 g deionized water, and 25 g tetramethylammonium hydroxide were mixed and stirred at room temperature for 10 min. 2 g aluminum isopropoxide was added, and the mixture was stirred at room temperature for 30 min until a gel formed. 2 g tetraethyl silicate was added, and the mixture was stirred at room temperature for 30 min. The resulting mixture was placed in a polytetrafluoroethylene reactor and heated at 200 °C under a nitrogen atmosphere for 4 h. After cooling to room temperature, the mixture was filtered, washed, and dried to obtain 4A molecular sieve adsorbent.

[0079] Carbon monoxide adsorption was tested using the molecular sieve in this comparative example on an IGA intelligent gravimetric analyzer. The purity of carbon monoxide in the gas was 99.9%. The adsorbent activity test conditions were: temperature 25℃, pressure range 0–1000 mbar. Adsorption tests were conducted on an IGA intelligent gravimetric analyzer filled with 4A molecular sieve adsorbent, and the mass change within the sample tube was detected. The test results for the 4A molecular sieve adsorbent were... Figure 2 The information is provided in the text.

[0080] Comparative Example 2

[0081] 0.2 g sodium hydroxide, 4 g deionized water, and 25 g tetramethylammonium hydroxide were mixed and stirred at room temperature for 10 min. 0.78 g aluminum hydroxide was added, and the mixture was stirred at room temperature for 30 min until a gel formed. 2 g tetraethyl silicate was added, and the mixture was stirred at room temperature for 30 min. The resulting mixture was placed in a polytetrafluoroethylene reactor and heated at 200 °C under a nitrogen atmosphere for 4 h. After cooling to room temperature, the mixture was filtered, washed, and dried to obtain 4A molecular sieve adsorbent.

[0082] Carbon monoxide adsorption was tested using the molecular sieve in this comparative example on an IGA intelligent gravimetric analyzer. The purity of carbon monoxide in the gas was 99.9%. The adsorbent activity test conditions were: temperature 25℃, pressure range 0–1000 mbar. Adsorption tests were conducted on an IGA intelligent gravimetric analyzer filled with 4A molecular sieve adsorbent, and the mass change within the sample tube was detected. The test results for the 4A molecular sieve adsorbent were... Figure 2 The information is provided in the text.

[0083] Comparative Example 3

[0084] 0.2 g sodium hydroxide, 4 g deionized water, and 25 g tetramethylammonium hydroxide were mixed and stirred at room temperature for 10 min. 2 g aluminum isopropoxide was added, and the mixture was stirred at room temperature for 30 min until a gel formed. 0.6 g fumed silica was added, and the mixture was stirred at room temperature for 30 min. The resulting mixture was placed in a polytetrafluoroethylene reactor and heated at 200 °C under a nitrogen atmosphere for 4 h. After cooling to room temperature, the mixture was filtered, washed, and dried to obtain 4A molecular sieve adsorbent.

[0085] Carbon monoxide adsorption was tested using the molecular sieve in this comparative example on an IGA intelligent gravimetric analyzer. The purity of carbon monoxide in the gas was 99.9%. The adsorbent activity test conditions were: temperature 25℃, pressure range 0–1000 mbar. Adsorption tests were conducted on an IGA intelligent gravimetric analyzer filled with 4A molecular sieve adsorbent, and the mass change within the sample tube was detected. The test results for the 4A molecular sieve adsorbent were... Figure 2 The information is provided in the text.

[0086] Comparative Example 4

[0087] 0.2 g sodium hydroxide, 4 g deionized water, and 25 g tetramethylammonium hydroxide were mixed and stirred at room temperature for 10 min. 2 g aluminum isopropoxide was added, and the mixture was stirred at room temperature for 30 min until a gel formed. 0.84 g silica sol was added, and the mixture was stirred at room temperature for 30 min. The resulting mixture was placed in a polytetrafluoroethylene reactor and heated at 200 °C under a nitrogen atmosphere for 4 h. After cooling to room temperature, the mixture was filtered, washed, and dried to obtain 4A molecular sieve adsorbent.

[0088] Carbon monoxide adsorption was tested using the molecular sieve in this comparative example on an IGA intelligent gravimetric analyzer. The purity of carbon monoxide in the gas was 99.9%. The adsorbent activity test conditions were: temperature 25℃, pressure range 0–1000 mbar. Adsorption tests were conducted on an IGA intelligent gravimetric analyzer filled with 4A molecular sieve adsorbent, and the mass change within the sample tube was detected. The test results for the 4A molecular sieve adsorbent were... Figure 2 The information is provided in the text.

[0089] Comparative Example 5

[0090] 0.2 g sodium hydroxide, 4 g deionized water, and 25 g tetramethylammonium hydroxide were mixed and stirred at room temperature for 10 min. 2 g aluminum isopropoxide was added, and the mixture was stirred at room temperature for 30 min until a gel formed. 2 g tetraethyl silicate was added, and the mixture was stirred at room temperature for 30 min. The resulting mixture was placed in a polytetrafluoroethylene reactor and heated at 200 °C under a nitrogen atmosphere for 4 h, then cooled to room temperature; filtered, washed, and dried to obtain 4A molecular sieve adsorbent. The obtained 4A molecular sieve adsorbent was impregnated in 25 mL of a solution containing 0.3 g copper nitrate for 3 h, filtered, and dried. The resulting mixture was treated at 200 °C under a nitrogen atmosphere for 2 h to obtain Cu(Ⅰ) / 4A molecular sieve adsorbent.

[0091] Carbon monoxide adsorption was tested using the molecular sieve of this comparative example on an IGA intelligent gravimetric analyzer. The purity of carbon monoxide in the gas was 99.9%. The adsorbent activity test conditions were: temperature 25℃, pressure range 0–1000 mbar. Adsorption tests were conducted on an IGA intelligent gravimetric analyzer filled with Cu(Ⅰ) / 4A molecular sieve adsorbent, and the mass change in the sample tube was detected. The test results of Cu(Ⅰ) / 4A molecular sieve adsorbent were as follows: Figure 2 The results are given in [the document]. Five regeneration tests were conducted on the Cu(I) / 4A molecular sieve adsorbent, and the results are [determined]. Figure 5 The information is provided in the text.

[0092] Table 1. Component addition amounts in each embodiment

[0093]

[0094]

[0095] Table 2 shows the regeneration performance tests of some examples and comparative examples.

[0096]

[0097] As shown in Table 1, compared to the 4A molecular sieve adsorbent, the Cu(I)-loaded 4A molecular sieve adsorbent, i.e., the Cu(I) / 4A molecular sieve adsorbent, increased the CO adsorption capacity. Compared to the Cu(I) / 4A molecular sieve adsorbent obtained by high-temperature reduction of Cu(II), the Cu(I) / 4A molecular sieve adsorbent obtained by reduction with a reducing agent in this application also increased the CO adsorption capacity. As shown in Table 2, compared to the Cu(I) / 4A molecular sieve adsorbent obtained by high-temperature reduction of Cu(II), the Cu(I) / 4A molecular sieve adsorbent obtained by reduction with a reducing agent in this application showed improved regeneration performance. This is because the technical solution provided in this application utilizes the π-complexation of carbon monoxide and monovalent copper to form π-complex bonds. By introducing copper, the pore size of the Cu(I) / 4A molecular sieve adsorbent obtained is slightly larger than the molecular dynamic diameter of carbon monoxide, effectively solving the problems of poor regeneration stability and low adsorption capacity, and achieving better technical results.

[0098] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0099] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A method of making a Cu(I) / 4A molecular sieve adsorbent characterized by, The method comprises: (1) first stirring and mixing a copper salt and an organic amine to obtain a first mixture; (2) second stirring and mixing sodium hydroxide and deionized water into the first mixture to obtain a second mixture; (3) third stirring and mixing an aluminum source into the second mixture to obtain a third mixture; (4) fourth stirring and mixing a silicon source into the third mixture to obtain a fourth mixture; (5) performing a crystallization reaction on the fourth mixture, and after cooling to room temperature, performing filtration, washing and first drying to obtain a Cu(I) / 4A molecular sieve adsorbent precursor; (6) performing a reduction reaction on the Cu(I) / 4A molecular sieve adsorbent precursor and a reducing agent, and after cooling to room temperature, performing filtration, washing and second drying to obtain a Cu(I) / 4A molecular sieve adsorbent. In step (1), the organic amine comprises tetramethylammonium hydroxide.

2. The method of claim 1, wherein, The mass ratio of the copper salt, the organic amine, the sodium hydroxide, the deionized water, the aluminum source, the silicon source, the reducing agent is (0.1-0.5):(15-30):(0.1-0.3):(3-5):(0.5-3):(0.5-3):(0.05-0.1).

3. The method according to claim 1 or 2, characterized in that, In step (1), the copper salt comprises one or more of copper nitrate, copper sulfate and copper chloride.

4. The method according to claim 1 or 2, characterized in that, In step (1), the first stirring and mixing comprises stirring at room temperature for 10-30 min.

5. The method according to claim 1 or 2, characterized in that, In step (2), the second stirring and mixing comprises stirring at room temperature for 10-30 min.

6. The method of claim 1 or 2, wherein, In step (3), the aluminum source comprises one or more of aluminum isopropoxide and aluminum hydroxide.

7. The method of claim 1 or 2, wherein, In step (3), the third stirring and mixing comprises stirring at room temperature for 10-30 min.

8. The method of claim 1 or 2, wherein, In step (4), the silicon source comprises one or more of tetraethyl orthosilicate, fumed silica or silica sol.

9. The method of claim 1 or 2, wherein, In step (4), the fourth stirring and mixing comprises stirring at room temperature for 10-30 min.

10. The method of claim 1, wherein, In step (5), the crystallization reaction comprises loading the fourth mixture into a polytetrafluoroethylene reactor, and crystallizing at 100-200℃ for 3-5 h.

11. The method according to claim 1 or 10, characterized in that, In step (6), the reduction reaction comprises mixing and grinding the Cu(I) / 4A molecular sieve adsorbent precursor and the reducing agent, and heating at 100-200℃ under a nitrogen atmosphere for 4 h.

12. The method of claim 1 or 10, wherein, In step (6), the reducing agent comprises one or more of VCl3 or sodium sulfite.

13. A Cu(I) / 4A molecular sieve adsorbent characterized by, The Cu(I) / 4A molecular sieve adsorbent is prepared by the method of any one of claims 1-12.

14. Use of the Cu(I) / 4A molecular sieve adsorbent of claim 13, characterized in that, The Cu(I) / 4A molecular sieve adsorbent is used for adsorbing and separating carbon monoxide.

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